Semiconductor device

ABSTRACT

To suppress a change in electrical characteristics and to improve reliability in a semiconductor device using a transistor including an oxide semiconductor. The semiconductor device includes a gate electrode over an insulating surface, an oxide semiconductor film overlapping with the gate electrode, a gate insulating film which is between the gate electrode and the oxide semiconductor film and is in contact with a surface of the oxide semiconductor film, a protective film in contact with an opposite surface of the surface of the oxide semiconductor film, and a pair of electrodes in contact with the oxide semiconductor film. In the gate insulating film or the protective film, the amount of gas having a mass-to-charge ratio m/z of 17 released by heat treatment is greater than the amount of nitrogen oxide released by heat treatment.

TECHNICAL FIELD

The present invention relates to an object, a method, or a manufacturingmethod. In addition, the present invention relates to a process, amachine, manufacture, or a composition of matter. In particular, thepresent invention relates to a semiconductor device, a display device, alight-emitting device, a power storage device, a storage device, adriving method thereof, or a manufacturing method thereof. Furthermore,in particular, the present invention relates to a semiconductor deviceincluding a field-effect transistor.

In this specification and the like, a semiconductor device generallymeans a device that can function by utilizing semiconductorcharacteristics. A semiconductor element such as a transistor, asemiconductor circuit, an arithmetic device, and a memory device areeach one embodiment of a semiconductor device. An imaging device, adisplay device, a liquid crystal display device, a light-emittingdevice, an electro-optical device, a power generation device (includinga thin film solar cell, an organic thin film solar cell, and the like),and an electronic device may each include a semiconductor device.

BACKGROUND ART

Transistors used for most flat panel displays typified by a liquidcrystal display device and a light-emitting display device are formedusing silicon semiconductors such as amorphous silicon, single crystalsilicon, and polycrystalline silicon provided over glass substrates.Further, such a transistor employing such a silicon semiconductor isused in integrated circuits (ICs) and the like.

In recent years, attention has been drawn to a technique in which,instead of a silicon semiconductor, a metal oxide exhibitingsemiconductor characteristics is used in transistors. Note that in thisspecification, a metal oxide exhibiting semiconductor characteristics isreferred to as an oxide semiconductor.

For example, a technique is disclosed in which a transistor ismanufactured using zinc oxide or an In-Ga-Zn-based oxide as an oxidesemiconductor and the transistor is used as a switching element or thelike of a pixel of a display device (see Patent Documents 1 and 2).

It has been pointed out that hydrogen is a supply source of carriersparticularly in an oxide semiconductor. Therefore, some measures need tobe taken to prevent hydrogen from entering the oxide semiconductor atthe time of forming the oxide semiconductor. Further, variation in athreshold voltage is suppressed by reducing the amount of hydrogencontained in the oxide semiconductor film or a gate insulating film incontact with the oxide semiconductor (see Patent Document 3).

REFERENCE Patent Documents

[Patent Document 1] Japanese Published Patent Application No.2007-123861

[Patent Document 2] Japanese Published Patent Application No.2007-096055

[Patent Document 3] Japanese Published Patent Application No.2009-224479

DISCLOSURE OF INVENTION

However, similarly to hydrogen, nitrogen becomes a source for supplyingcarriers. Thus, when a large amount of nitrogen is contained in a filmin contact with an oxide semiconductor film, the electricalcharacteristics, for a typical example, the threshold voltage, of atransistor including the oxide semiconductor film is changed. Further,there is a problem in that electrical characteristics vary among thetransistors.

One object of one embodiment of the present invention is to suppress achange in electrical characteristics and to improve reliability in asemiconductor device using a transistor including an oxidesemiconductor. Another object of one embodiment of the present inventionis to provide a semiconductor device with low power consumption. Anotherobject of one embodiment of the present invention is to provide a novelsemiconductor device or the like. Note that the descriptions of theseobjects do not disturb the existence of other objects. In one embodimentof the present invention, there is no need to achieve all the objects.Other objects will be apparent from and can be derived from thedescription of the specification, the drawings, the claims, and thelike.

One embodiment of the present invention is a semiconductor deviceincluding a gate electrode over an insulating surface, an oxidesemiconductor film overlapping with the gate electrode, a gateinsulating film which is between the gate electrode and the oxidesemiconductor film and is in contact with a surface of the oxidesemiconductor film, a protective film in contact with an oppositesurface of the surface of the oxide semiconductor film, and a pair ofelectrodes in contact with the oxide semiconductor film. The gateinsulating film or the protective film has a region where the amount ofgas having a mass-to-charge ratio m/z of 17 released by heat treatmentis greater than the amount of nitrogen oxide released by heat treatment.

One embodiment of the present invention is a semiconductor deviceincluding a transistor having a gate electrode over an insulatingsurface, an oxide semiconductor film overlapping with the gateelectrode, a gate insulating film which is between the gate electrodeand the oxide semiconductor film and is in contact with a surface of theoxide semiconductor film, a protective film in contact with an oppositesurface of the surface of the oxide semiconductor film, and a pair ofelectrodes in contact with the oxide semiconductor film. In a log-loggraph showing the amount of change in threshold voltage of thetransistor with respect to stress time, a space of a logarithmic scaleon a lateral axis is equal to that on a longitudinal axis, an anglebetween a power approximation line of the absolute values of the amountof change in threshold voltage and a straight line indicating that theabsolute values of the amount of change in the threshold voltage is 0 Vis greater than or equal to −3° and less than 20°, and the absolutevalue of the amount of change in the threshold voltage when the stresstime is 0.1 hours is smaller than 0.3 V. Note that the stress time meansa time during which a load such as voltage or temperature is applied tothe transistor.

One embodiment of the present invention is a semiconductor deviceincluding a transistor having a gate electrode over an insulatingsurface, an oxide semiconductor film overlapping with the gateelectrode, a gate insulating film which is between the gate electrodeand the oxide semiconductor film and is in contact with a surface of theoxide semiconductor film, a protective film in contact with an oppositesurface of the surface of the oxide semiconductor film, and a pair ofelectrodes in contact with the oxide semiconductor film. In a graphshowing the amount of change in the threshold voltage of the transistorwith respect to stress time, an index of a power approximation line ofthe amount of change in threshold voltage is greater than or equal to−0.1 and less than or equal to 0.3, and the amount of change in thethreshold voltage when the stress time is 0.1 hours is smaller than 0.3V.

The gate insulating film or the protective film may have a region or aportion whose spin density measured by electron spin resonance (ESR)spectroscopy is less than 1×10¹⁸ spins/cm³, preferably greater than orequal to 1×10¹⁷ spins/cm³ and less than 1×10¹⁸ spins/cm³.

The gate insulating film or the protective film has a region or aportion where, in an electron spin resonance spectrum, a first signalthat appears at a g-factor of greater than or equal to 2.037 and lessthan or equal to 2.039, a second signal that appears at a g-factor ofgreater than or equal to 2.001 and less than or equal to 2.003, and athird signal that appears at a g-factor of greater than or equal to1.964 and less than or equal to 1.966 are observed. The split width ofthe first and second signals and the split width of the second and thirdsignals that are obtained by measurement using an X-band are eachapproximately 5 mT.

In the electron spin resonance spectrum of the gate insulating film orthe protective film, a signal attributed to nitrogen oxide may beobserved. The nitrogen oxide may contain nitrogen monoxide or nitrogendioxide.

The protective film, the oxide semiconductor film, and the gateinsulating film may be between the insulating surface and the gateelectrode. Alternatively, the gate electrode and the gate insulatingfilm may be between the insulating surface and the oxide semiconductorfilm.

The pair of electrodes may be between the oxide semiconductor film andthe protective film. Alternatively, the pair of electrodes may bebetween the oxide semiconductor film and the gate insulating film.

One embodiment of the present invention can suppress a change inelectrical characteristics of a transistor including an oxidesemiconductor film and improve reliability. One embodiment of thepresent invention can provide a semiconductor device with less powerconsumption. One embodiment of the present invention can provide a novelsemiconductor device or the like. Note that the descriptions of theseeffects do not disturb the existence of other effects. In one embodimentof the present invention, there is no need to obtain all the effects.Other effects will be apparent from and can be derived from thedescription of the specification, the drawings, the claims, and thelike.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A to 1C illustrate one embodiment of a transistor.

FIG. 2 is a graph showing the absolute values of the amount of change inthe threshold voltage of a transistor after a BT stress test.

FIGS. 3A to 3D illustrate one embodiment of a method for forming atransistor.

FIGS. 4A and 4B each illustrate one embodiment of a transistor.

FIGS. 5A and 5B each illustrate one embodiment of a transistor.

FIGS. 6A to 6C illustrate one embodiment of a transistor.

FIGS. 7A to 7F each illustrate one embodiment of a transistor.

FIGS. 8A to 8C each show a band structure of a transistor.

FIG. 9 illustrates one embodiment of a transistor.

FIGS. 10A to 10C illustrate one embodiment of a transistor.

FIGS. 11A and 11B illustrate the relationship between formation energyand transition levels and electron configurations of defects.

FIG. 12 illustrates a change in the Fermi level and a change in thecharge states of defects.

FIG. 13 shows a crystalline model of c-SiO₂.

FIG. 14 shows a model in which NO₂ is introduced into an interstitialsite of a c-SiO₂ model.

FIG. 15 shows a model in which N₂O is introduced into an interstitialsite of a c-SiO₂ model.

FIG. 16 shows a model in which NO is introduced into an interstitialsite of a c-SiO₂ model.

FIG. 17 shows a model in which an N atom is introduced into aninterstitial site of a c-SiO₂ model.

FIG. 18 is a band diagram.

FIGS. 19A and 19B each show a model of a cluster structure.

FIGS. 20A and 20B show ESR spectra of NO₂ and N—Si—N.

FIG. 21 illustrates a mechanism of a phenomenon in which the thresholdvoltage of a transistor is shifted in the positive direction.

FIGS. 22A to 22D illustrate bulk models.

FIG. 23 illustrates a structure of a model.

FIGS. 24A and 24B illustrate the relationship between the formationenergy and transition levels of VoH and the thermodynamic transitionlevel of VoH.

FIG. 25 shows the relationship between the carrier density and thedefect density of VoH.

FIG. 26 illustrates a band structure of DOS inside an oxidesemiconductor film and in the vicinity of the interface of the oxidesemiconductor film.

FIG. 27 is a graph showing deterioration of a transistor including anoxide semiconductor film in a dark state.

FIG. 28 illustrates deterioration of a transistor including an oxidesemiconductor film in a dark state.

FIG. 29 is a graph showing deterioration of a transistor including anoxide semiconductor film under light irradiation.

FIG. 30 illustrates showing deterioration of a transistor including anoxide semiconductor film under light irradiation.

FIG. 31 is a graph showing deterioration of a transistor including anoxide semiconductor film under light irradiation.

FIGS. 32A to 32F illustrate a model where an oxide semiconductor film ishighly purified to be intrinsic.

FIGS. 33A to 33C illustrate a crystalline model of InGaZnO₄ and adefect.

FIGS. 34A and 34B illustrate a structure of a model in which a C atom isput in an interstitial site (6) and its density of states.

FIGS. 35A and 35B illustrate a structure of a model in which an In atomis replaced with a C atom and its density of states.

FIGS. 36A and 36B illustrate a structure of a model in which a Ga atomis replaced with a C atom and its density of states.

FIGS. 37A and 37B illustrate a structure of a model in which a Zn atomis replaced with a C atom and its density of states.

FIGS. 38A to 38C are a top view and cross-sectional views illustratingone embodiment of a transistor.

FIGS. 39A to 39D are cross-sectional views illustrating one embodimentof a method for manufacturing a transistor.

FIGS. 40A and 40B are each a cross-sectional view of one embodiment of atransistor.

FIGS. 41A to 41C are a top view and cross-sectional views illustratingone embodiment of a transistor.

FIGS. 42A to 42C illustrate a structure of a display panel of oneembodiment.

FIG. 43 illustrates one embodiment of a display device.

FIG. 44 illustrates one embodiment of a display device.

FIG. 45 illustrates a display module.

FIGS. 46A to 46D each illustrate an electronic device of one embodiment.

FIGS. 47A to 47C show TDS analysis results.

FIGS. 48A to 48C show TDS analysis results.

FIGS. 49A and 49B show TDS analysis results.

FIG. 50 shows TDS analysis results.

FIGS. 51A and 51B show SIMS analysis results.

FIGS. 52A to 52C show TDS analysis results.

FIGS. 53A to 53C show TDS analysis results.

FIGS. 54A and 54B show SIMS analysis results.

FIGS. 55A and 55B show SIMS analysis results.

FIGS. 56A to 56C show ESR measurement results.

FIGS. 57A to 57C show ESR measurement results.

FIG. 58 shows V_(g)-I_(d) characteristics of transistors.

FIG. 59 shows the amount of change in threshold voltage and the amountof change in shift value of transistors after gate BT stress tests andafter gate BT photostress tests.

FIG. 60 shows V_(g)-I_(d) characteristics of transistors.

FIG. 61 shows the amount of change in threshold voltage and the amountof change in shift value of transistors after gate BT stress tests andafter gate BT photostress tests.

FIG. 62 shows the amount of change in spin density and the amount ofchange in threshold voltage.

FIGS. 63A to 63E are cross-sectional views each illustrating oneembodiment of a transistor.

FIGS. 64A to 64D each shows V_(g)-I_(d) characteristics of a transistor.

FIG. 65 shows the absolute values of the amounts of change in thethreshold voltages of transistors after a BT stress test.

FIG. 66 shows the changes in the threshold voltages of transistors inrepeating ±BT stress tests.

FIGS. 67A and 67B show results of SIMS analysis.

FIGS. 68A and 68B show ESR measurement results.

FIGS. 69A and 69B show TDS analysis results.

FIGS. 70A to 70C are cross-sectional TEM images and a local Fouriertransform image of an oxide semiconductor.

FIGS. 71A and 71B show nanobeam electron diffraction patterns of oxidesemiconductor films and FIGS. 71C and 71D illustrate an example of atransmission electron diffraction measurement apparatus.

FIG. 72A shows an example of structural analysis by transmissionelectron diffraction measurement and FIGS. 72B and 72C show plan-viewTEM images.

FIGS. 73A to 73D are Cs-corrected high-resolution TEM images of a crosssection of a CAAC-OS and a cross-sectional schematic view of a CAAC-OS.

FIGS. 74A to 74D are Cs-corrected high-resolution TEM images of a planeof a CAAC-OS.

FIGS. 75A to 75C show structural analysis of a CAAC-OS and a singlecrystal oxide semiconductor by XRD.

FIGS. 76A and 76B show electron diffraction patterns of a CAAC-OS.

FIG. 77 shows a change in crystal part of an In—Ga—Zn oxide induced byelectron irradiation.

FIGS. 78A and 78B are schematic views showing deposition models of aCAAC-OS and an nc-OS.

FIGS. 79A to 79C show an InGaZnO₄ crystal and a pellet.

FIGS. 80A to 80D are schematic views showing a deposition model of aCAAC-OS.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention are described below in detail withreference to the drawings. Note that the present invention is notlimited to the following description, and it is easily understood bythose skilled in the art that the mode and details can be variouslychanged without departing from the spirit and scope of the presentinvention. Therefore, the present invention should not be construed asbeing limited to the description in the following embodiments andexamples. In addition, in the following embodiments and examples, thesame portions or portions having similar functions are denoted by thesame reference numerals or the same hatching patterns in differentdrawings, and description thereof is not repeated.

Note that in each drawing described in this specification, the size, thefilm thickness, or the region of each component is exaggerated forclarity in some cases. Therefore, embodiments of the present inventionare not limited to such a scale.

In addition, terms such as “first”, “second”, and “third” in thisspecification are used in order to avoid confusion among components, andthe terms do not limit the components numerically. Therefore, forexample, the term “first” can be replaced with the term “second”,“third”, or the like as appropriate.

In this specification, the term “parallel” indicates that the angleformed between two straight lines is greater than or equal to −10° andless than or equal to 10°, and accordingly also includes the case wherethe angle is greater than or equal to −5° and less than or equal to 5°.The term “perpendicular” indicates that the angle formed between twostraight lines is greater than or equal to 80° and less than or equal to100°, and accordingly includes the case where the angle is greater thanor equal to 85° and less than or equal to 95°.

In this specification, trigonal and rhombohedral crystal systems areincluded in a hexagonal crystal system.

Functions of a “source” and a “drain” are sometimes replaced with eachother when the direction of current flow is changed in circuitoperation, for example. Therefore, the terms “source” and “drain” can beused to denote the drain and the source, respectively, in thisspecification.

Note that a voltage refers to a difference between potentials of twopoints, and a potential refers to electrostatic energy (electricpotential energy) of a unit charge at a given point in an electrostaticfield. Note that in general, a difference between a potential of onepoint and a reference potential (e.g., a ground potential) is merelycalled a potential or a voltage, and a potential and a voltage are usedas synonymous words in many cases. Thus, in this specification, apotential may be rephrased as a voltage and a voltage may be rephrasedas a potential unless otherwise specified.

Note that a transistor including an oxide semiconductor film is ann-channel transistor; therefore, in this specification, a transistorthat can be regarded as having no drain current flowing therein when agate voltage is 0 V is defined as a transistor having normally-offcharacteristics. In contrast, a transistor that can be regarded ashaving a drain current flowing therein when the gate voltage is 0 V isdefined as a transistor having normally-on characteristics.

Note that the channel length refers to, for example, a distance betweena source (source region or source electrode) and a drain (drain regionor drain electrode) in a region where an oxide semiconductor film (or aportion where a current flows in an oxide semiconductor film when atransistor is on) and a gate electrode overlap with each other or aregion where a channel is formed in a top view of the transistor. In onetransistor, channel lengths in all regions are not necessarily the same.In other words, the channel length of one transistor is not limited toone value in some cases. Therefore, in this specification, the channellength is any one of values, the maximum value, the minimum value, orthe average value in a region where a channel is formed.

The channel width refers to, for example, the length of a portion wherea source and a drain face each other in a region where an oxidesemiconductor film (or a portion where a current flows in an oxidesemiconductor film when a transistor is on) and a gate electrode overlapwith each other or a region where a channel is formed. In onetransistor, channel widths in all regions are not necessarily the same.In other words, the channel width of one transistor is not limited toone value in some cases. Therefore, in this specification, the channelwidth is any one of values, the maximum value, the minimum value, or theaverage value in a region where a channel is formed.

Note that depending on transistor structures, a channel width in aregion where a channel is formed actually (hereinafter referred to as aneffective channel width) is different from a channel width shown in atop view of a transistor (hereinafter referred to as an apparent channelwidth) in some cases. For example, in a transistor having athree-dimensional structure, an effective channel width is greater thanan apparent channel width shown in a top view of the transistor, and itsinfluence cannot be ignored in some cases. For example, in aminiaturized transistor having a three-dimensional structure, theproportion of a channel region formed in a side surface of an oxidesemiconductor film is higher than the proportion of a channel regionformed in a top surface of the oxide semiconductor film in some cases.In that case, an effective channel width obtained when a channel isactually formed is greater than an apparent channel width shown in thetop view.

In a transistor having a three-dimensional structure, an effectivechannel width is difficult to measure in some cases. For example,estimation of an effective channel width from a design value requires anassumption that the shape of an oxide semiconductor film is known.Therefore, in the case where the shape of an oxide semiconductor film isnot known accurately, it is difficult to measure an effective channelwidth accurately.

Therefore, in this specification, in a top view of a transistor, anapparent channel width that is a length of a portion where a source anda drain face each other in a region where an oxide semiconductor filmand a gate electrode overlap with each other is referred to as asurrounded channel width (SCW) in some cases. Furthermore, in thisspecification, in the case where the term “channel width” is simplyused, it may denote a surrounded channel width or an apparent channelwidth. Alternatively, in this specification, in the case where the term“channel width” is simply used, it may denote an effective channel widthin some cases. Note that the values of a channel length, a channelwidth, an effective channel width, an apparent channel width, asurrounded channel width, and the like can be determined by obtainingand analyzing a cross-sectional TEM image and the like.

Note that in the case where field-effect mobility, a current value perchannel width, and the like of a transistor are obtained by calculation,a surrounded channel width may be used for the calculation. In thatcase, the values may be different from those calculated using aneffective channel width in some cases.

(Embodiment 1)

In this embodiment, a semiconductor device of one embodiment of thepresent invention and a method for manufacturing the semiconductordevice are described with reference to drawings. A transistor 10described in this embodiment has a bottom-gate structure.

<1. Structure of Transistor>

FIGS. 1A to 1C are a top view and cross-sectional views of thetransistor 10 included in a semiconductor device. FIG. 1A is a top viewof the transistor 10, FIG. 1B is a cross-sectional view taken alongdashed-dotted line A-B in FIG. 1A, and FIG. 1C is a cross-sectional viewtaken along dashed-dotted line C-D in FIG. 1A. Note that in FIG. 1A, asubstrate 11, a gate insulating film 15, a protective film 21, and thelike are omitted for simplicity.

The transistor 10 illustrated in FIGS. 1A to 1C includes a gateelectrode 13 over the substrate 11, the gate insulating film 15 over thesubstrate 11 and the gate electrode 13, an oxide semiconductor film 17overlapping with the gate electrode 13 with the gate insulating film 15therebetween, and a pair of electrodes 19 and 20 in contact with theoxide semiconductor film 17. The protective film 21 is formed over thegate insulating film 15, the oxide semiconductor film 17, and the pairof electrodes 19 and 20.

The protective film 21 is in contact with a surface of the oxidesemiconductor film 17 that is an opposite side of a surface in contactwith the gate insulating film 15. Accordingly, the protective film 21has a function of protecting a region (hereinafter referred to as a backchannel region) of the oxide semiconductor film 17 that is on theopposite side of a region where a channel is formed.

In this embodiment, a film in contact with the oxide semiconductor film17, typically, at least one of the gate insulating film 15 and theprotective film 21 is an oxide insulating film containing nitrogen andhaving a small number of defects.

Typical examples of the oxide insulating film containing nitrogen andhaving a small number of defects include a silicon oxynitride film andan aluminum oxynitride film. Note that a “silicon oxynitride film” or an“aluminum oxynitride film” refers to a film that contains more oxygenthan nitrogen, and a “silicon nitride oxide film” or an “aluminumnitride oxide film” refers to a film that contains more nitrogen thanoxygen.

The oxide insulating film containing nitrogen and having a small numberof defects has a region or a portion where the amount of gas having amass-to-charge ratio m/z of 17 released by heat treatment is greaterthan the amount of nitrogen oxide (NO_(x), where x is greater than orequal to 0 and less than or equal to 2, preferably greater than or equalto 1 and less than or equal to 2) released by heat treatment. Typicalexamples of nitrogen oxide include nitrogen monoxide and nitrogendioxide. Alternatively, the oxide insulating film containing nitrogenand having a small number of defects has a region or a portion where theamount of gas having a mass-to-charge ratio m/z of 17 released by heattreatment is greater than the amount of gas having a mass-to-chargeratio m/z of 30 released by heat treatment. Alternatively, the oxideinsulating film containing nitrogen and having a small number of defectshas a region or a portion where the amount of gas having amass-to-charge ratio m/z of 17 released by heat treatment is greaterthan the amount of gas having a mass-to-charge ratio m/z of 46 releasedby heat treatment. Alternatively, the oxide insulating film containingnitrogen and having a small number of defects has a region or a portionwhere the amount of gas having a mass-to-charge ratio m/z of 17 releasedby heat treatment is greater than the sum of the amount of gas having amass-to-charge ratio m/z of 30 and the amount of gas having amass-to-charge ratio m/z of 46 released by heat treatment. Note that inthis specification, the amount of gas released by heat treatment is, forexample, the amount of gas released by heat treatment with which thesurface temperature of a film becomes higher than or equal to 50° C. andlower than or equal to 650° C., preferably higher than or equal to 50°C. and lower than or equal to 550° C.

Further alternatively, the oxide insulating film containing nitrogen andhaving a small number of defects has a region or a portion where theamount of gas having a mass-to-charge ratio m/z of 30 released by heattreatment is less than or equal to the detection limit and where theamount of gas having a mass-to-charge ratio m/z of 17 released by heattreatment is greater than or equal to 1×10¹⁸ molecules/cm³ and less thanor equal to 5×10¹⁹ molecules/cm³. Alternatively, the oxide insulatingfilm containing nitrogen and having a small number of defects has aregion or a portion where the amount of gas having a mass-to-chargeratio m/z of 46 released by heat treatment is less than or equal to thedetection limit and where the amount of gas having a mass-to-chargeratio m/z of 17 released by heat treatment is greater than or equal to1×10¹⁸ molecules/cm³ and less than or equal to 5×10¹⁹ molecules/cm³.Alternatively, the oxide insulating film containing nitrogen and havinga small number of defects has a region or a portion where the amount ofgas having a mass-to-charge ratio m/z of 30 released by heat treatmentis less than or equal to the detection limit, where the amount of gashaving a mass-to-charge ratio m/z of 46 released by heat treatment isless than or equal to the detection limit, and where the amount of gashaving a mass-to-charge ratio m/z of 17 released by heat treatment isgreater than or equal to 1×10¹⁸ molecules/cm³ and less than or equal to5×10¹⁹ molecules/cm³.

A typical example of the gas having a mass-to-charge ratio m/z of 30includes nitrogen monoxide. A typical example of the gas having amass-to-charge ratio m/z of 17 includes ammonia. A typical example ofthe gas having a mass-to-charge ratio m/z of 46 includes nitrogendioxide. The amount of gas released by heat treatment is measured bythermal desorption spectroscopy (TDS), for example.

A method for measuring the amount of released gas by TDS analysis isdescribed below. Here, the measurement method of the amount of moleculesx released is described as an example.

The amount of a released gas in TDS analysis is proportional to theintegral value of a spectrum obtained by the analysis. Therefore, theamount of a released gas can be calculated from the ratio between theintegral value of a spectrum of an insulating film and the referencevalue of a standard sample. The reference value of a standard samplerefers to the ratio of the density of a predetermined atom contained ina sample to the integral value of a spectrum.

For example, the amount of molecules x (N_(x)) released from aninsulating film can be found according to Formula 1 with the TDSanalysis results of a silicon wafer containing hydrogen at apredetermined density which is the standard sample and the TDS analysisresults of the insulating film. Note that all spectra at mass-to-chargeratios which are obtained by the TDS analysis here are assumed tooriginate from the molecules x.N_(O2)=N_(H2)/S_(H2)×S_(x)×α_(x)   [Formula 1]

Note that N_(H2) is the value obtained by conversion of the amount ofhydrogen molecules released from the standard sample into density, andS_(H2) is the integral value of a spectrum when the standard sample issubjected to TDS analysis. Here, the reference value of the standardsample is set to N_(H2)/S_(H2). The value S_(x) is the integral value ofa spectrum when the insulating film is subjected to TDS analysis. Notethat α_(x) (x is a kind of molecule) is a coefficient affecting theintensity of the spectrum in the TDS analysis and depends on the kind ofmolecule. For details of Formula 1, refer to Japanese Published PatentApplication No. H6-275697. The amount of molecules x released from theabove insulating film is measured with a thermal desorption spectroscopyapparatus produced by ESCO Ltd., EMD-WA1000S/W using a silicon wafercontaining hydrogen atoms at 9.62×10¹⁶ atoms/cm² as the standard sample.

Further, in Formula 1, an integral value of spectrum when the amount ofreleased nitrogen monoxide, nitrogen dioxide, or ammonia is measured bythe TDS analysis is substituted into S_(x), whereby the amount ofreleased nitrogen monoxide, nitrogen dioxide, or ammonia can beobtained.

Note that in the TDS analysis, the detection limit of the amount ofreleased gas having a mass-to-charge ratio m/z of 30 (nitrogen monoxide)is 1×10¹⁷ molecules/cm³, 5×10¹⁶ molecules/cm³, 4×10¹⁶ molecules/cm³, or1×10¹⁶ molecules/cm³.

In the TDS analysis, the detection limit of the amount of released gashaving a mass-to-charge ratio m/z of 46 (nitrogen dioxide) is 1×10¹⁷molecules/cm³, 5×10¹⁶ molecules/cm³, 4×10¹⁶ molecules/cm³, or 1×10¹⁶molecules/cm³.

In the TDS analysis, the detection limit of the amount of released gashaving a mass-to-charge ratio m/z of 17 (ammonia) is 5×10¹⁷molecules/cm³ or 1×10¹⁷ molecules/cm³.

In the case where a sample contains water, the spectrum of the sample isdivided into three fragments: mass-to-charge ratios of 18, 17, and 16.Note that fragmentation pattern coefficients can be obtained from theintensity ratio of the mass-to-charge ratios. The fragmentation patterncoefficients of mass-to-charge ratios of 18, 17, and 16 are 100, 23, and1, respectively. This means that in the spectrum for a mass-to-chargeratio of 17, the intensity of the sum of the amounts of released ammoniaand water is observed. Thus, the amount of ammonia released can beobtained by subtracting 0.23 times the amount of released gas having amass-to-charge ratio m/z of 18 from the amount of released gas having amass-to-charge ratio m/z of 17 in TDS analysis. Note that the amount ofreleased gas having a mass-to-charge ratio m/z of 17 described in thisspecification means the amount of only ammonia released and does notinclude the amount of water released.

Note that when an oxide insulating film where the amount of ammoniareleased by heat treatment is greater than the amount of nitrogen oxidereleased by heat treatment (such an oxide insulating film is typified byan oxide insulating film where the amount of released gas having amass-to-charge ratio m/z of 17 is greater than or equal to 1×10¹⁸molecules/cm³ and less than or equal to 5×10¹⁹ molecules/cm³) is used asthe protective film 21, Reaction Formulae (A-1) and (A-2) are satisfiedand nitrogen oxide is released as a nitrogen gas by heat treatment inthe manufacturing process. As a result, the nitrogen concentration andthe content of nitrogen oxide in the protective film 21 can be reduced.Furthermore, carrier traps at the interface between the gate insulatingfilm 15 or the protective film 21 and the oxide semiconductor film 17can be reduced. In addition, a change in the threshold voltage of thetransistor included in the semiconductor device can be reduced, whichleads to a reduction in change in the electrical characteristics of thetransistor.NO+4NH₃+O₂→4N₂+6H₂O   (A-1)2NO₂+4NH₃+O₂→3N₂+6H₂O   (A-2)

In an ESR spectrum at 100 K or lower of the oxide insulating filmcontaining nitrogen and having a small number of defects, after heattreatment, a first signal that appears at a g-factor of greater than orequal to 2.037 and less than or equal to 2.039, a second signal thatappears at a g-factor of greater than or equal to 2.001 and less than orequal to 2.003, and a third signal that appears at a g-factor of greaterthan or equal to 1.964 and less than or equal to 1.966 are observed. Thesplit width of the first and second signals and the split width of thesecond and third signals that are obtained by ESR measurement using anX-band are each approximately 5 mT. The sum of the spin densities of thefirst signal that appears at a g-factor of greater than or equal to2.037 and less than or equal to 2.039, the second signal that appears ata g-factor of greater than or equal to 2.001 and less than or equal to2.003, and the third signal that appears at a g-factor of greater thanor equal to 1,964 and less than or equal to 1.966 is lower than 1×10¹⁸spins/cm³, typically higher than or equal to 1×10¹⁷ spins/cm³ and lowerthan 1×10¹⁸ spins/cm³.

In the ESR spectrum at 100 K or lower, the first signal that appears ata g-factor of greater than or equal to 2.037 and less than or equal to2.039, the second signal that appears at a g-factor of greater than orequal to 2.001 and less than or equal to 2.003, and the third signalthat appears at a g-factor of greater than or equal to 1.964 and lessthan or equal to 1.966 correspond to signals attributed to nitrogenoxide (NO_(x); x is greater than or equal to 0 and less than or equal to2, preferably greater than or equal to 1 and less than or equal to 2).Typical examples of nitrogen oxide include nitrogen monoxide andnitrogen dioxide. In other words, the lower the total spin density ofthe first signal that appears at a g-factor of greater than or equal to2.037 and less than or equal to 2.039, the second signal that appears ata g-factor of greater than or equal to 2.001 and less than or equal to2.003, and the third signal that appears at a g-factor of greater thanor equal to 1.964 and less than or equal to 1.966 is, the lower thecontent of nitrogen oxide in the oxide insulating film is.

At least one of the gate insulating film 15 and the protective film 21preferably has a nitrogen concentration measured by secondary ion massspectrometry (SIMS) of lower than or equal to 6×10²⁰ atoms/cm³. In thatcase, nitrogen oxide is unlikely to be generated in at least one of thegate insulating film 15 and the protective film 21, so that the carriertrap at the interface between the oxide semiconductor film 17 and thegate insulating film 15 or the interface between the oxide semiconductorfilm 17 and the protective film 21 can be inhibited. Furthermore, achange in the threshold voltage of the transistor included in thesemiconductor device can be reduced, which leads to a reduced change inthe electrical characteristics of the transistor.

FIG. 2 shows a power approximation line L1 indicating the absolutevalues of the amount of change in the threshold voltage (|ΔV_(th)|) ofthe transistor 10 with respect to test time (hereinafter, also referredto as stress time) between before and after a gate BT stress test inwhich positive voltage or negative voltage is applied to the gate of thetransistor 10. In the transistor 10, the gate insulating film 15 or theprotective film 21 includes an oxide insulating film containing nitrogenand having a small number of defects. When test time (stress time) andthe amount of change in the threshold voltage are plotted on a graph,the plotted values can be approximated by a power approximation line.The power approximation line is a straight line in a log-log graph. Notethat in a log-log graph, the index of a power approximation linecorresponds to the slope of a straight line. FIG. 2 is a log-log graph.The lateral axis indicates a logarithm of stress time and thelongitudinal axis indicates a logarithm of the absolute value of theamount of change in the threshold voltage. In the case of using adisplay device as a semiconductor device, for example, the followingconditions can be used for the stress test: the maximum temperature is60° C.; the maximum driving voltage is 30 V; and the stress is appliedfor a given period of time e.g., 100 hours).

A measurement method of the gate BT stress test is described. First,substrate temperature is kept constant at given temperature(hereinafter, referred to as stress temperature) to measure the initialV_(g)-I_(d) characteristics of the transistor.

Next, while the substrate temperature is kept at stress temperature, thepair of electrodes serving as a source electrode and a drain electrodeof the transistor is set at the same potential and the gate electrode issupplied with a potential different from that of the pair of electrodesfor a certain period of time (hereinafter referred to as stress time).Then, the V_(g)-I_(d) characteristics of the transistor are measuredwhile the substrate temperature is kept at the stress temperature. As aresult, a difference in threshold voltage and a difference in shiftvalue between before and after the gate BT stress test can be obtainedas the amount of change in the electrical characteristics.

Note that a stress test where negative voltage is applied to a gateelectrode is called negative gate BT stress test (dark negative stress);whereas a stress test where positive voltage is applied is calledpositive gate BT stress test (dark positive stress). Note that a stresstest where negative voltage is applied to a gate electrode while lightemission is performed is called negative gate BT photostress test(negative photostress); whereas a stress test where positive voltage isapplied while light emission is performed is called positive gate BTphotostress test (positive photostress).

Since the power approximation line L1 is a straight line in the log-loggraph of FIG. 2, when the space of the logarithmic scale on the lateralaxis is equal to that on the longitudinal axis, an angle θ1 between thepower approximation line L1 of the transistor 10 described in thisembodiment and a straight line (a dashed line L2 in FIG. 2) having anindex of power function of 0, indicating that threshold voltage is notchanged with respect to stress time, is in a range of θ2. In addition,when stress time is 0.1 hours, |ΔV_(th)| is less than 0.3 V, preferablyless than 0.1 V. Note that θ2 is an angle between dashed-dotted linesand is typified by an angle in a range from 3° in a negative directionto 20° in a positive direction from a straight line indicating ⊕ΔV_(th)|of 0.1 V; in other words, the angle is greater than or equal to −3° andless than 20°, preferably greater than or equal to 0° and less than 15°.Note that the description that “the space of the logarithmic scale onthe lateral axis is equal to that on the longitudinal axis” means that,for example, the interval between 0.01 hours to 0.1 hours on the lateralaxis (stress time becomes 10 times) is the same as the interval between0.01 V to 0.1 V on the longitudinal axis (ΔV_(th) becomes 10 times).Here, the positive direction for 2θ is a counterclockwise direction.

As in the transistor 10 described in this embodiment, as the angle θ1between the power approximation line L1, which indicates the absolutevalues of the amount of change in threshold voltage (|ΔV_(th)) withrespect to stress time, and the dashed line L2 is small, a transistorhas a smaller amount of change in threshold voltage over time and higherreliability.

In FIG. 2, when the lateral axis is x and the longitudinal axis is y,the power approximation line L1 can be represented by Formula 2. Notethat b and C are each a constant, and b corresponds to the index of thepower approximation line L1.y=Cx^(b)   [Formula 2]

In the transistor 10 described in this embodiment, the index b of thepower approximation line L1 is greater than or equal to −0.1 and lessthan or equal to 0.3, preferably greater than or equal to 0 and lessthan or equal to 0.2, and ΔV_(th) when the stress time is 0.1 hours isless than 0.3 V, preferably less than 0.1 V.

As the index b of the power approximation line L1 is smaller, atransistor has a smaller amount of change in the threshold voltage overtime and higher reliability. As ΔV_(th) when the stress time is 0.1hours is smaller, a transistor has higher reliability at initialoperation. As a result, a transistor in which the index b of the powerapproximation line L1 is greater than or equal to −0.1 and less than orequal to 0.3, preferably greater than or equal to 0 and less than orequal to 0.2, and ΔV_(th) when the stress time is 0.1 hours is smallerthan 0.3 V, preferably smaller than 0.1 V has high reliability.

When at least one of the gate insulating film 15 and the protective film21 in contact with the oxide semiconductor film 17 contains a smallamount of nitrogen oxide as described above, the carrier trap at theinterface between the oxide semiconductor film 17 and the gateinsulating film 15 or the interface between the oxide semiconductor film17 and the protective film 21 can be inhibited. As a result, a change inthe threshold voltage of the transistor included in the semiconductordevice can be reduced, which leads to a reduced change in the electricalcharacteristics of the transistor.

The details of other components of the transistor 10 are describedbelow.

There is no particular limitation on the property of a material and thelike of the substrate 11 as long as the material has heat resistanceenough to withstand at least later heat treatment. A variety ofsubstrates can be used as the substrate 11 to form a transistor, forexample. The type of a substrate is not limited to a certain type.Examples of the substrate include a semiconductor substrate (e.g., asingle crystal substrate or a silicon substrate), an SOI substrate, aglass substrate, a quartz substrate, a plastic substrate, a metalsubstrate, a stainless steel substrate, a substrate including stainlesssteel foil, a tungsten substrate, a substrate including tungsten foil, aflexible substrate, an attachment film, paper including a fibrousmaterial, and a base material film. As an example of a glass substrate,a barium borosilicate glass substrate, an aluminoborosilicate glasssubstrate, soda lime glass substrate, or the like can be given. Examplesof a flexible substrate, an attachment film, a base material film, orthe like are as follows: plastic typified by polyethylene terephthalate(PET), polyethylene naphthalate (PEN), and polyether sulfone (PES); asynthetic resin such as acrylic; polypropylene; polyester; polyvinylfluoride; polyvinyl chloride; polyester; polyamide; polyimide; aramid;epoxy; an inorganic vapor deposition film; and paper. Specifically, whena transistor is formed using a semiconductor substrate, a single crystalsubstrate, an SOI substrate, or the like, it is possible to form atransistor with few variations in characteristics, size, shape, or thelike, with high current supply capability, and with a small size. Byforming a circuit with the use of such a transistor, power consumptionof the circuit can be reduced or the circuit can be highly integrated.

Alternatively, a flexible substrate may be used as the substrate 11, andthe transistor 10 may be provided directly on the flexible substrate.Further alternatively, a separation layer may be provided between thesubstrate 11 and the transistor 10. The separation layer can be usedwhen part or the whole of a semiconductor device formed over theseparation layer is separated front the substrate 11 and transferredonto another substrate. In such a case, the transistor 10 can betransferred to a substrate having low heat resistance or a flexiblesubstrate as well. For the above separation layer, a stack includinginorganic films, which are a tungsten film and a silicon oxide film, oran organic resin film of polyimide or the like formed over a substratecan be used, for example.

Examples of a substrate to which a transistor is transferred include, inaddition to the above-described substrates over which transistors can beformed, a paper substrate, a cellophane substrate, an aramid filmsubstrate, a polyimide film substrate, a stone substrate, a woodsubstrate, a cloth substrate (including a natural fiber (e.g., silk,cotton, or hemp), a synthetic fiber (e.g., nylon, polyurethane, orpolyester), a regenerated fiber (e.g., acetate, cupra, rayon, orregenerated polyester), or the like), a leather substrate, a rubbersubstrate, and the like. With the use of such a substrate, a transistorwith excellent properties or a transistor with low power consumption canbe formed, a device with high durability and high heat resistance can beprovided, or a reduction in weight or thickness can be achieved.

A base insulating film may be provided between the substrate 11 and thegate electrode 13. Examples of the base insulating film include asilicon oxide film, a silicon oxynitride film, a silicon nitride film, asilicon nitride oxide film, a gallium oxide film, a hafnium oxide film,an yttrium oxide film, an aluminum oxide film, and an aluminumoxynitride film. Note that when silicon nitride, gallium oxide, hafniumoxide, yttrium oxide, aluminum oxide, or the like is used for the baseinsulating film, it is possible to suppress diffusion of impurities suchas alkali metal, water, and hydrogen from the substrate 11 into theoxide semiconductor film 17.

The gate electrode 13 can be formed using a metal element selected fromaluminum, chromium, copper, tantalum, titanium, molybdenum, nickel,iron, cobalt, and tungsten; an alloy containing any of these metalelements as a component; an alloy containing these metal elements incombination; or the like. Further, one or more metal elements selectedfrom manganese and zirconium may be used. The gate electrode 13 may havea single-layer structure or a layered structure of two or more layers.For example, any of the following can be used: a single-layer structureof an aluminum film containing silicon; a single-layer structure of acopper film containing manganese; two-layer structure in which atitanium film is stacked over an aluminum film; a two-layer structure inwhich a titanium film is stacked over a titanium nitride film; atwo-layer structure in which a tungsten film is stacked over a titaniumnitride film; a two-layer structure in which a tungsten film is stackedover a tantalum nitride film or a tungsten nitride film; a two-layerstructure in which a copper film is stacked over a copper filmcontaining manganese; a three-layer structure in which a titanium film,an aluminum film, and a titanium film are stacked in this order; athree-layer structure in which a copper film containing manganese, acopper film, and a copper film containing manganese are stacked in thisorder; and the like. Alternatively, an alloy film or a nitride filmwhich contains aluminum and one or more elements selected from titanium,tantalum, tungsten, molybdenum, chromium, neodymium, and scandium may beused.

The gate electrode 13 can also be formed using a light-transmittingconductive material such as indium tin oxide, indium oxide containingtungsten oxide, indium zinc oxide containing tungsten oxide, indiumoxide containing titanium oxide, indium tin oxide containing titaniumoxide, indium zinc oxide, or indium tin oxide containing silicon oxide.It is also possible to have a layered structure formed using the abovelight-transmitting conductive material and the above metal element.

In the case where the protective film 21 is formed using an oxideinsulating film containing nitrogen and having a small number ofdefects, the gate insulating film 15 can be formed to have asingle-layer structure or a stacked-layer structure using, for example,any of silicon oxide, silicon oxynitride, silicon nitride oxide, siliconnitride, aluminum oxide, hafnium oxide, gallium oxide, Ga-Zn-based metaloxide, and the like. Note that an oxide insulating film is preferablyused for at least a region of the gate insulating film 15, which is incontact with the oxide semiconductor film 17, in order to improvecharacteristics of the interface with the oxide semiconductor film 17.

Furthermore, it is possible to prevent outward diffusion of oxygen fromthe oxide semiconductor film 17 and entry of hydrogen, water, or thelike into the oxide semiconductor film 17 from the outside by providingan insulating film having a blocking effect against oxygen, hydrogen,water, and the like as the gate insulating film 15. As the insulatingfilm having a blocking effect against oxygen, hydrogen, water, and thelike, an aluminum oxide film, an aluminum oxynitride film, a galliumoxide film, a gallium oxynitride film, an yttrium oxide film, an yttriumoxynitride film, a hafnium oxide film, and a hafnium oxynitride film canbe given as examples.

The gate insulating film 15 may be formed using a high-k material suchas hafnium silicate (HfSiO_(x)), hafnium silicate to which nitrogen isadded (HfSi_(x)O_(y)N_(z)), hafnium aluminate to which nitrogen is added(HfAl_(x)O_(y)N_(z)), hafnium oxide, or yttrium oxide, so that gateleakage current of the transistor can be reduced.

The thickness of the gate insulating film 15 is greater than or equal to5 nm and less than or equal to 400 nm, preferably greater than or equalto 10 nm and less than or equal to 300 nm, further preferably greaterthan or equal to 50 nm and less than or equal to 250 nm.

The oxide semiconductor film 17 is formed using a metal oxide filmcontaining at least In or Zn; as a typical example, an In—Ga oxide film,an In—Zn oxide film, or an In—M—Zn oxide film (Al is Al, Ga, Y, Zr, La,Ce, or Nd) can be given.

Note that in the case where the oxide semiconductor film 17 contains anIn—M—Zn oxide, the proportions of In and ill when summation of In and Alis assumed to be 100 atomic % are preferably as follows: the proportionof In is greater than 25 atomic % and the proportion of M is less than75 atomic %, or further preferably, the proportion of In is greater than34 atomic % and the proportion of M is less than 66 atomic %.

The energy gap of the oxide semiconductor film 17 is 2 eV or more,preferably 2.5 eV or more, further preferably 3 eV or more. With the useof an oxide semiconductor having such a wide energy gap, the off-statecurrent of the transistor 10 can be reduced.

The thickness of the oxide semiconductor film 17 is greater than orequal to 3 nm and less than or equal to 200 nm, preferably greater thanor equal to 3 nm and less than or equal to 100 nm, further preferablygreater than or equal to 3 nm and less than or equal to 50 nm.

In the case where the oxide semiconductor film 17 contains an In—Al—Znoxide (M represents Al, Ga, Y, Zr, La, Ce, or Nd), it is preferable thatthe atomic ratio of metal elements of a sputtering target used forforming a film of the In—M—Zn oxide satisfy In M and Zn≥V. As the atomicratio of metal elements of such a sputtering target, In:M:Zn=1:1:1,1:1:1.2, and In:M:Zn=3:1:2 are preferable. Note that the atomic ratiosof metal elements in the formed oxide semiconductor film 17 vary fromthe above atomic ratio of metal elements of the sputtering target withina range of ±40% as an error.

Hydrogen contained in the oxide semiconductor reacts with oxygen bondedto a metal atom to be water, and causes oxygen vacancies in a lattice(or a portion) from which oxygen is released. Due to entry of hydrogeninto the oxygen vacancy, an electron serving as a carrier is generated.Further, in some cases, bonding of part of hydrogen to oxygen bonded toa metal element causes generation of an electron serving as a carrier.Thus, a transistor including an oxide semiconductor that containshydrogen is likely to be normally on.

Accordingly, it is preferable that hydrogen be reduced as much aspossible as well as the oxygen vacancies in the oxide semiconductor film17. Specifically, in the oxide semiconductor film 17, the hydrogenconcentration that is measured by secondary ion mass spectrometry (SIMS)is set to 2×10²⁰ atoms/cm³ or lower, preferably 5×10¹⁹ atoms/cm³ orlower, further preferably 1×10¹⁹ atoms/cm³ or lower, further preferably5×10¹⁸ atoms/cm³ or lower, further preferably 1×10¹⁸ atoms/cm³ or lower,further preferably 5×10¹⁷ atoms/cm³ or lower, further preferably 1×10¹⁶atoms/cm³ or lower. As a result, the transistor 10 has positivethreshold voltage (normally-off characteristics).

When silicon or carbon that is one of elements belonging to Group 14 iscontained in the oxide semiconductor film 17, oxygen vacancies areincreased in the oxide semiconductor film 17, and the oxidesemiconductor film 17 becomes an n-type film. Thus, the concentration ofsilicon or carbon (the concentration is measured by SIMS) of the oxidesemiconductor film 17 is lower than or equal to 2×10¹⁸ atoms/cm³,preferably lower than or equal to 2×10¹⁷ atoms/cm³. As a result, thetransistor 10 has positive threshold voltage (normally-offcharacteristics).

Furthermore, the concentration of alkali metal or alkaline earth metalof the oxide semiconductor film 17, which is measured by SIMS, is lowerthan or equal to 1×10¹⁸ atoms/cm³, preferably lower than or equal to2×10¹⁶ atoms/cm³. Alkali metal and alkaline earth metal might generatecarriers when bonded to an oxide semiconductor, in which case theoff-state current of the transistor might be increased. Thus, it ispreferable to reduce the concentration of alkali metal or alkaline earthmetal of the oxide semiconductor film 17. As a result, the transistor 10has positive threshold voltage (normally-off characteristics).

Furthermore, when containing nitrogen, the oxide semiconductor film 17easily becomes an n-type film by generation of electrons serving ascarriers and an increase of carrier density, Thus, a transistorincluding an oxide semiconductor that contains nitrogen is likely to benormally on. For this reason, nitrogen in the oxide semiconductor filmis preferably reduced as much as possible; the concentration of nitrogenthat is measured by SIMS is preferably set to, for example, lower thanor equal to 5×10¹⁸ atoms/cm³.

When impurities in the oxide semiconductor film 17 are reduced, thecarrier density of the oxide semiconductor film 17 can be lowered. Theoxide semiconductor preferably has a carrier density of 1×10¹⁷ /cm³ orless, further preferably 1×10¹⁵/cm³ or less, still further preferably1×10¹³ /cm³ or less, yet still further preferably 1×10¹¹/cm³ or less.

Note that it is preferable to use, as the oxide semiconductor film 17,an oxide semiconductor film in which the impurity concentration is lowand density of defect states is low, in which case the transistor canhave more excellent electrical characteristics. Here, the state in whichimpurity concentration is low and density of detect states is low (thenumber of oxygen vacancies is small) is referred to as “highly purifiedintrinsic” or “substantially highly purified intrinsic”. A transistorformed using a highly purified intrinsic or substantially highlypurified intrinsic oxide semiconductor has few carrier generationsources, and thus has a low carrier density in some cases. Thus, atransistor including the oxide semiconductor film in which a channelregion is formed is likely to have positive threshold voltage(normally-off characteristics). A transistor including a highly purifiedintrinsic or substantially highly purified intrinsic oxide semiconductorfilm has a low density of defect states and accordingly has a low trapstate in some cases. Furthermore, a highly purified intrinsic orsubstantially highly purified intrinsic oxide semiconductor film has anextremely low off-state current; the off-state current can be less thanor equal to the measurement limit of a semiconductor parameter analyzer,i.e., less than or equal to 1×10⁻¹³ A, at a voltage (drain voltage)between a source electrode and a drain electrode of from 1 V to 10 V.Thus, the transistor whose channel region is formed in the oxidesemiconductor film has a small variation in electrical characteristicsand high reliability in some cases.

The oxide semiconductor film 17 may have a non-single-crystal structure,for example. The non-single crystal structure includes a c-axis alignedcrystalline oxide semiconductor (CAAC-OS) that is described later, apolycrystalline structure, a microcrystalline structure described later,or an amorphous structure, for example. Among the non-single crystalstructure, the amorphous structure has the highest density of defectlevels, whereas CAAC-OS has the lowest density of defect levels.

Note that the oxide semiconductor film 17 may be a mixed film includingtwo or more of the following: a region having an amorphous structure, aregion having a microcrystalline structure, a region having apolycrystalline structure, a region of CAAC-OS described later, and aregion having a single-crystal structure. The mixed film has asingle-layer structure including, for example, two or more of a regionhaving an amorphous structure, a region having a microcrystallinestructure, a region having a polycrystalline structure, a CAAC-OSregion, and a region having a single-crystal structure in some cases.Further, the mixed film has a stacked-layer structure of two or more ofa region having an amorphous structure, a region having amicrocrystalline structure, a region having a polycrystalline structure,a CAAC-OS region, and a region having a single-crystal structure in somecases.

The pair of electrodes 19 and 20 is formed with a single-layer structureor a layered structure using any of metals such as aluminum, titanium,chromium, nickel, copper, yttrium, zirconium, molybdenum, iron, cobalt,silver, tantalum, and tungsten and an alloy containing any of thesemetals as a main component. For example, a single-layer structure of analuminum film containing silicon; a single-layer structure of a copperfilm containing manganese; a two-layer structure in which an aluminumfilm is stacked over a titanium film; a two-layer structure in which analuminum film is stacked over a tungsten film; a two-layer structure inwhich a copper film is stacked over a copper-magnesium-aluminum alloyfilm; a two-layer structure in which a copper film is stacked over atitanium film; a two-layer structure in which a copper film is stackedover a tungsten film; a two-layer structure in which a copper film isstacked over a copper film containing manganese; a three-layer structurein which a titanium film or a titanium nitride film, an aluminum film ora copper film, and a titanium film or a titanium nitride film arestacked in this order; a three-layer structure in which a molybdenumfilm or a molybdenum nitride film, an aluminum film or a copper film,and a molybdenum film or a molybdenum nitride film are stacked in thisorder; a three-layer structure in which a copper film containingmanganese, a copper film, and a copper film containing manganese arestacked in this order; and the like can be given. Note that atransparent conductive material containing indium oxide, tin oxide, orzinc oxide may be used.

Note that although the pair of electrodes 19 and 20 is provided betweenthe oxide semiconductor film 17 and the protective film 21 in thisembodiment, the pair of electrodes 19 and 20 may be provided between thegate insulating film 15 and the oxide semiconductor film 17.

When the gate insulating film 15 is formed of an oxide insulating filmcontaining nitrogen and having a small number of defects, the protectivefilm 21 can be formed using silicon oxide, silicon oxynitride,Ga-Zn-based metal oxide, or the like.

Further, it is possible to prevent outward diffusion of oxygen from theoxide semiconductor film 17 and entry of hydrogen, water, or the likeinto the oxide semiconductor film 17 from the outside by providing aninsulating film having a blocking effect against oxygen, hydrogen,water, and the like as the protective film 21. As for the insulatingfilm having a blocking effect against oxygen, hydrogen, water, and thelike, an aluminum oxide film, an aluminum oxynitride film, a galliumoxide film, a oxynitride film, an yttrium oxide film, an yttriumoxynitride film, a hafnium oxide film, a hafnium oxynitride film, and asilicon nitride film, can be given as examples.

The protective film 21 includes a region with a thickness greater thanor equal to 50 nm and less than or equal to 1000 nm, preferably greaterthan or equal to 150 nm and less than or equal to 400 nm.

<2. Method for Manufacturing Transistor>

Next, a method for manufacturing the transistor 10 in FIGS. 1A to 1C isdescribed with reference to FIGS. 3A to 3D. A cross-section in thechannel length direction along dot-dashed line A-B in FIG. 1A and across-section in the channel width direction along dot-dashed line C-Din FIG. 1A are used in FIGS. 3A to 3D to describe the method formanufacturing the transistor 10.

The films included in the transistor 10 (i.e., the insulating film, theoxide semiconductor film, the metal oxide film, the conductive film, andthe like) can be formed by any of a sputtering method, a chemical vapordeposition (CVD) method, a vacuum evaporation method, and a pulsed laserdeposition (PLD) method. Alternatively, a coating method or a printingmethod can be used. Although the sputtering method and a plasma-enhancedchemical vapor deposition (PECVD) method are typical examples of thefilm formation method, a thermal CVD method may be used. As the thermalCVD method, a metal organic chemical vapor deposition (MOCVD) method oran atomic layer deposition (ALD) method may be used, for example.

Deposition by the thermal CVD method may be performed in such a mannerthat the pressure in a chamber is set to an atmospheric pressure or areduced pressure, and a source gas and an oxidizer are supplied to thechamber at a time and react with each other in the vicinity of thesubstrate or over the substrate. Thus, no plasma is generated in thedeposition; therefore, the thermal CVD method has an advantage that nodefect due to plasma damage is caused.

Deposition by the ALD method may be performed in such a manner that thepressure in a chamber is set to an atmospheric pressure or a reducedpressure, source gases for reaction are sequentially introduced into thechamber, and then the sequence of the gas introduction is repeated. Forexample, two or more kinds of source gases are sequentially supplied tothe chamber by switching respective switching valves (also referred toas high-speed valves). In such a case, a first source gas is introduced,an inert gas (e.g., argon or nitrogen) or the like is introduced at thesame time or after the first source gas is introduced so that the sourcegases are not mixed, and then a second source gas is introduced. Notethat in the case where the first source gas and the inert gas areintroduced at a time, the inert gas serves as a carrier gas, and theinert gas may also be introduced at the same time as the second sourcegas. Alternatively, the first source gas may be exhausted by vacuumevacuation instead of the introduction of the inert gas, and then thesecond source gas may be introduced. The first source gas is adsorbed onthe surface of the substrate to form a first single-atomic layer; thenthe second source gas is introduced to react with the firstsingle-atomic layer; as a result, a second single-atomic layer isstacked over the first single-atomic layer, so that a thin film isformed.

The sequence of the gas introduction is repeated plural times until adesired thickness is obtained, whereby a thin film with excellent stepcoverage can be formed. The thickness of the thin film can be adjustedby the number of repetition times of the sequence of the gasintroduction; therefore, the ALD method makes it possible to accuratelyadjust a thickness and thus is suitable for manufacturing a minute FET.

As illustrated in FIG. 3A, the gate electrode 13 is formed over thesubstrate 11.

A formation method of the gate electrode 13 is described below. First, aconductive film is formed by a sputtering method, a vacuum evaporationmethod, a pulsed laser deposition (PLD) method, a thermal CND method, orthe like and then a mask is formed over the conductive film by aphotolithography process. Next, the conductive film is partly etchedusing the mask to form the gate electrode 13. After that, the mask isremoved.

Note that the gate electrode 13 may be formed by an electrolytic platingmethod, a printing method, an ink-jet method, or the like instead of theabove formation method.

Alternatively, a tungsten film can be formed as the conductive film witha deposition apparatus employing ALD. In that case, a WF₆ gas and a B₂H₆gas are sequentially introduced more than once to form an initialtungsten film, and then a WF₆ gas and an H₂ gas are introduced at atime, so that a tungsten film is formed. Note that an SiH₄ gas may beused instead of a B₂H₆ gas.

Here, a 100-nm-thick tungsten film is formed by a sputtering method.Next, a mask is formed by a photolithography process, and the tungstenfilm is subjected to dry etching with the use of the mask to form thegate electrode 13.

Then, the gate insulating film 15 is formed over the substrate 11 andthe gate electrode 13, and the oxide semiconductor film 17 is formed ina region that is over the gate insulating film 15 and overlaps with thegate electrode 13.

The gate insulating film 15 is formed by a sputtering method, a CVDmethod, a vacuum evaporation method, a pulsed laser deposition (PLD)method, a thermal CVD method, or the like.

In the case of forming a silicon oxide film or a silicon oxynitride filmas the gate insulating film 15, a deposition gas containing silicon andan oxidizing gas are preferably used as a source gas. Typical examplesof the deposition gas containing silicon include silane, disilane,trisilane, and silane fluoride. Examples of the oxidizing gas includeoxygen, ozone, dinitrogen monoxide, and nitrogen dioxide.

In the case where a gallium oxide film is formed as the gate insulatingfilm 15, an MOCVD method can be used.

In the case where a hafnium oxide film is formed as the gate insulatingfilm 15 by a thermal CVD method such as an MOCVD method or an ALDmethod, two kinds of gases, i.e., ozone (O₃) as an oxidizer and a sourcematerial gas which is obtained by vaporizing liquid containing a solventand a hafnium precursor compound (a hafnium alkoxide solution, which istypified by tetrakis(dimethylamide)hafnium (TDMAH)), are used. Note thatthe chemical formula of tetrakis(dimethylamide)hafnium is Hf[N(CH₃)₂]₄.Examples of another material liquid includetetrakis(ethymethylamide)hafnium.

In the case where an aluminum oxide film is formed as the gateinsulating film 15 by a thermal CVD method such as an MOCVD method or anALD method, two kinds of gases, i.e., H₂O as an oxidizer and a sourcematerial gas which is obtained by vaporizing liquid containing a solventand an aluminum precursor compound (e.g., trimethylaluminum (TMA)) areused. Note that the chemical formula of trimethylaluminum is Al(CH₃)₃.Examples of another material liquid include tris(dimethylamide)aluminum,triisobutylaluminum, and aluminumtris(2,2,6,6-tetramethyl-3,5-heptanedionate).

Furthermore, in the case where a silicon oxide film is formed as thegate insulating film 15 by a thermal CVD method such as an MOCVD methodor an ALD method, hexachlorodisilane is adsorbed on a depositionsurface, chlorine contained in the adsorbate is removed, and radicals ofan oxidizing gas (e.g., O₂ or dinitrogen monoxide) are supplied to reactwith the adsorbate.

Here, a silicon oxynitride film is formed as the gate insulating film 15by a plasma CVD method.

A formation method of the oxide semiconductor film 17 is describedbelow. An oxide semiconductor film is formed over the gate insulatingfilm 15 by a sputtering method, a coating method, a pulsed laserdeposition method, a laser ablation method, a thermal CVD method, or thelike. Then, after a mask is formed over the oxide semiconductor film bya photolithography process, the oxide semiconductor film is partlyetched using the mask. Accordingly, the oxide semiconductor film 17 thatis over the gate insulating film 15 and subjected to element isolationso as to partly overlap with the gate electrode 13 is formed asillustrated in FIG. 3B. After that, the mask is removed.

Alternatively, by using a printing method for forming the oxidesemiconductor film 17, the oxide semiconductor film 17 subjected toelement isolation can be formed directly.

As a power supply device for generating plasma in the case of formingthe oxide semiconductor film by a sputtering method, an RF power supplydevice, an AC power supply device, a DC power supply device, or the likecan be used as appropriate.

As a sputtering gas, a rare gas (typically argon), an oxygen gas, or amixed gas of a rare gas and an oxygen gas is used as appropriate. In thecase of the mixed gas of a rare gas and an oxygen gas, the proportion ofoxygen to a rare gas is preferably increased.

Further, a target may be appropriately selected in accordance with thecomposition of the oxide semiconductor film to be formed.

For example, in the case where the oxide semiconductor film is formed bya sputtering method at a substrate temperature higher than or equal to150° C. and lower than or equal to 750° C., preferably higher than orequal to 150° C. and lower than or equal to 450° C., further preferablyhigher than or equal to 200° C. and lower than or equal to 350° C., theoxide semiconductor film can be a CAAC-OS film.

For the deposition of the CAAC-OS film, the following conditions arepreferably used.

By suppressing entry of impurities into the CAAC-OS film during thedeposition, the crystal state can be prevented from being broken by theimpurities. For example, the concentration of impurities e.g., hydrogen,water, carbon dioxide, or nitrogen) that exist in the deposition chambermay be reduced. Furthermore, the concentration of impurities in adeposition gas may be reduced. Specifically, a deposition gas whose dewpoint is −80° C. or lower, preferably −100° C.; or lower is used.

Furthermore, it is preferable that the proportion of oxygen in thedeposition gas be increased and the power be optimized in order toreduce plasma damage at the deposition. The proportion of oxygen in thedeposition gas is higher than or equal to 30 vol %, preferably 100 vol%.

As an example of the sputtering target, an In-Ga-Zn-based metal oxidetarget is described below

After the oxide semiconductor film is formed, dehydrogenation ordehydration may be performed by heat treatment. The temperature of theheat treatment is typically higher than or equal to 150° C. and lowerthan the strain point of the substrate, preferably higher than or equalto 250° C. and lower than or equal to 450° C., further preferably higherthan or equal to 300° C. and lower than or equal to 450° C.

The heat treatment is performed under an inert gas atmosphere containingnitrogen or a rare gas such as helium, neon, argon, xenon, or krypton.Further, the heat treatment may be performed under an inert gasatmosphere first, and then under an oxygen atmosphere. It is preferablethat the above inert gas atmosphere and the above oxygen atmosphere donot contain hydrogen, water, and the like. The treatment time is 3minutes to 24 hours.

An electric furnace, an RTA apparatus, or the like can be used for theheat treatment. With the use of an RTA apparatus, the heat treatment canbe performed at a temperature higher than or equal to the strain pointof the substrate if the heating time is short. Therefore, the heattreatment time can be shortened.

By forming the oxide semiconductor film while it is heated or performingheat treatment after the formation of the oxide semiconductor film, thehydrogen concentration can be 5×10¹⁹ atoms/cm³ or lower, preferably1×10¹⁹ atoms/cm³ or lower, further preferably 5×10¹⁸ atoms/cm³ or lower,still further preferably 1×10¹⁸ atoms/cm³ or lower, yet still furtherpreferably 5×10¹⁷ atoms/cm³ or lower, yet still further preferably1×10¹⁶ atoms/cm³ or lower.

For example, in the case where an oxide semiconductor film, e.g., anInGaZnO_(x) (X>O) film is formed using a deposition apparatus employingALD, an In(CH₃)₃ gas and an O₃ gas are sequentially introduced two ormore times to form an InO₂ layer, a Ga(CH₃)₃ gas and an O₃ gas areintroduced at a time to form a GaO layer, and then a Zn(CH₃)₂ gas and anO₃ gas are introduced at a time to form a ZnO layer. Note that the orderof these layers is not limited to this example. A mixed compound layersuch as an InGaO₂ layer, an InZnO₂ layer, a GaInO layer, a ZnInO layer,or a GaZnO layer may be formed by mixing of these gases. Note thatalthough an H₂O gas which is obtained by bubbling with an inert gas suchas Ar may be used instead of an O₃ gas, it is preferable to use an O₃gas, which does not contain H. Instead of an In(CH₃)₃ gas, an In(C₂H₅)₃may be used. Instead of a Ga(CH₃)₃ gas, a Ga(C₂H₅)₃ gas may be used.Furthermore, a Zn(CH₃)₂ gas may be used.

Here, a 35-nm-thick oxide semiconductor film is formed by a sputteringmethod, a mask is formed over the oxide semiconductor film, and thenpart of the oxide semiconductor film is selectively etched. Then, afterthe mask is removed, heat treatment is performed in a mixed atmospherecontaining nitrogen and oxygen, whereby the oxide semiconductor film 17is formed.

When the heat treatment is performed at a temperature higher than 350°C. and lower than or equal to 650° C., preferably higher than or equalto 450° C. and lower than or equal to 600° C., it is possible to obtainan oxide semiconductor film whose proportion of CAAC, which is describedlater, is greater than or equal to 70% and less than 100%, preferablygreater than or equal to 80% and less than 100%, further preferablygreater than or equal to 90% and less than 100%, still furtherpreferably greater than or equal to 95% and less than or equal to 98%.Furthermore, it is possible to obtain an oxide semiconductor film havinga low content of hydrogen, water, and the like. This means that an oxidesemiconductor film with a low impurity concentration and a low densityof defect states can be formed.

Next, as illustrated in FIG. 3C, the pair of electrodes 19 and 20 areformed.

A method for forming the pair of electrodes 19 and 20 is describedbelow. First, a conductive film is formed by a sputtering method, avacuum evaporation method, a pulsed laser deposition (PLD) method, athermal CVD method, or the like. Then, a mask is formed over theconductive film by a photolithography process. After that, theconductive film is etched using the mask to form the pair of electrodes19 and 20. After that, the mask is removed.

Here, a 50-nm-thick tungsten film, a 400-nm-thick aluminum film, and a100-nm-thick titanium film are sequentially stacked by a sputteringmethod. Next, a mask is formed over the titanium film by aphotolithography process and the tungsten film, the aluminum film, andthe titanium film are thy-etched with use of the mask to form the pairof electrodes 19 and 20.

Note that heat treatment may be performed after the pair of electrodes19 and 20 are formed. For example, this heat treatment can be performedin a manner similar to that of the heat treatment performed after theoxide semiconductor film 17 is formed.

After the pair of electrodes 19 and 20 are formed, cleaning treatment ispreferably performed to remove an etching residue. A short circuit ofthe pair of electrodes 19 and 20 can be suppressed by this cleaningtreatment. The cleaning treatment can be performed using an alkalinesolution such as a tetramethylammonium hydroxide (TMAH) solution; anacidic solution such as a hydrofluoric acid, an oxalic acid solution, ora phosphoric acid solution; or water.

Next, the protective film 21 is formed over the oxide semiconductor film17 and the pair of electrodes 19 and 20. The protective film 21 can beformed by a sputtering method, a CVD method, an evaporation method, orthe like.

In the case where an oxide insulating film containing nitrogen andhaving a small number of defects is formed as the protective film 21, asilicon oxynitride film can be formed by a CVD method as an example ofthe oxide insulating film. In this case, a deposition gas containingsilicon and an oxidizing gas are preferably used as a source gas.Typical examples of the deposition gas containing silicon includesilane, trisilane, and silane fluoride. Examples of the oxidizing gasinclude dinitrogen monoxide and nitrogen dioxide.

The oxide insulating film containing nitrogen and having a small numberof defects can be formed by a CVD method under the conditions where theratio of an oxidizing gas to a deposition gas is higher than 20 timesand lower than 100 times, preferably higher than or equal to 40 timesand lower than or equal to 80 times and the pressure in a treatmentchamber is lower than 100 Pa, preferably lower than or equal to 50 Pa.

Here, a silicon oxynitride film is formed by a plasma CVD method underthe conditions where the substrate 11 is held at a temperature of 220°C., silane at a flow rate of 50 sccm and dinitrogen monoxide at a flowrate of 2000 sccm are used as a source gas, the pressure in thetreatment chamber is 20 Pa, and a high-frequency power of 100 W at 13.56MHz (1.6×10⁻² W/cm² as the power density) is supplied to parallel-plateelectrodes.

In the case where an oxide insulating film containing nitrogen andhaving a small number of defects is formed as the protective film 21,ammonia can be used as a source gas instead of a deposition gascontaining silicon or an oxidation gas. In that case, a film including aregion from which a large amount of gas having a mass-to-charge ratiom/z of 17 (ammonia as a typical example) is released can be formed.

A silicon oxynitride film is formed by, for example, a plasma CVD methodunder the conditions where the substrate 11 is held at a temperature of220° C., silane at a flow rate of 30 sccm, dinitrogen monoxide at a flowrate of 4000 sccm, and ammonia at a flow rate of 100 sccm are used as asource gas, the pressure in the treatment chamber is 40 Pa, and ahigh-frequency power of 150 W at 13.56 MHz (2.4×10⁻² W/cm² as the powerdensity) is supplied to parallel-plate electrodes.

Next, heat treatment may be performed. The temperature of the heattreatment is typically higher than or equal to 150° C. and lower thanthe strain point of the substrate, preferably higher than or equal to200° C. and lower than or equal to 450° C., further preferably higherthan or equal to 300° C. and lower than or equal to 450° C. By the heattreatment, water, hydrogen, and the like contained in the protectivefilm 21 can be released.

Here, heat treatment is performed at 350° C. in a mixed atmospherecontaining nitrogen and oxygen for one hour.

Next, another heat treatment may be performed. The temperature of theheat treatment is typically higher than or equal to 150° C. and lowerthan the strain point of the substrate, preferably higher than or equalto 200° C. and lower than or equal to 450° C., further preferably higherthan or equal to 300° C. and lower than or equal to 450° C.

Through the above steps, a transistor in which a change in thresholdvoltage is reduced can be manufactured. Further, a transistor in which achange in electrical characteristics is reduced can be manufactured.

<Modification Example 1>

Modification examples of the transistor 10 described in this embodimentare described with reference to FIGS. 4A and 4B. In each of thetransistors described in this modification example, a gate insulatingfilm or a protective film has a stacked-layer structure.

In a transistor using an oxide semiconductor, oxygen vacancies in anoxide semiconductor film cause defects of electrical characteristics ofthe transistor. For example, the threshold voltage of a transistorincluding an oxide semiconductor film that contains oxygen vacancies inthe film easily shifts in the negative direction, and such a transistortends to have normally-on characteristics. This is because charge isgenerated owing to the oxygen vacancies in the oxide semiconductor film,resulting in reduction of the resistance of the oxide semiconductorfilm.

Further, when an oxide semiconductor film includes oxygen vacancies,there is a problem in that the amount of change in electricalcharacteristics, for a typical example, the amount of change in thethreshold voltage of the transistor, is increased due to change overtime or a bias-temperature stress test (hereinafter also referred to asa BT stress test).

Thus, by forming an oxide insulating film containing oxygen at a higherproportion than oxygen in the stoichiometric composition as a part ofthe protective film, a transistor in which a shift of the thresholdvoltage in the negative direction is suppressed and that has excellentelectrical characteristics can be manufactured. In addition, a highlyreliable transistor in which a variation in electrical characteristicswith time or a variation in electrical characteristics due to a gate BTphotostress test is small can be manufactured.

In a transistor 10 a illustrated in FIG. 4A, the protective film 21 hasa multi-layer structure. Specifically, the protective film 21 includesan oxide insulating film 23, an oxide insulating film 25 containingoxygen at a higher proportion than oxygen in the stoichiometriccomposition, and a nitride insulating film 27. The oxide insulating film23 in contact with the oxide semiconductor film 17 is an oxideinsulating film containing nitrogen and having a small number of defectsthat can be used as at least one of the gate insulating film 15 and theprotective film 21 of the transistor 10.

The oxide insulating film 25 is formed using an oxide insulating filmthat contains oxygen at a higher proportion than oxygen in thestoichiometric composition. Part of oxygen is released by heating fromthe oxide insulating film containing oxygen at a higher proportion thanoxygen in the stoichiometric composition. The oxide insulating filmcontaining oxygen at a higher proportion than oxygen in thestoichiometric composition is an oxide insulating film of which theamount of released oxygen converted into oxygen atoms is greater than orequal to 1.0×10¹⁸ atoms/cm³, preferably greater than or equal to3.0×10²⁰ atoms/cm³ in TDS analysis. Note that the temperature of thefilm surface in the TDS analysis is preferably higher than or equal to100° C. and lower than or equal to 700° C., or higher than or equal to100° C. and lower than or equal to 500° C.

A silicon oxide film, a silicon oxynitride film, or the like with athickness greater than or equal to 30 nm and less than or equal to 500nm, or greater than or equal to 50 nm and less than or equal to 400 nmcan be used for the oxide insulating film 25.

As the oxide insulating film 25, a silicon oxide film or a siliconoxynitride film is formed under the following conditions: the substrateplaced in a treatment chamber of the plasma CVD apparatus that isvacuum-evacuated is held at a temperature higher than or equal to 180°C. and lower than or equal to 280° C., preferably higher than or equalto 200° C. and lower than or equal to 240° C., the pressure is greaterthan or equal to 100 Pa and less than or equal to 250 Pa, preferablygreater than or equal to 100 Pa and less than or equal to 200 Pa withintroduction of a source gas into the treatment chamber, and ahigh-frequency power of greater than or equal to 0.17 W/cm² and lessthan or equal to 0.5 W/cm², preferably greater than or equal to 0.25W/cm² and less than or equal to 0.35 W/cm² is supplied to an electrodeprovided in the treatment chamber.

As a source gas of the oxide insulating film 25, a deposition gascontaining silicon and an oxidizing gas is preferably used. Typicalexamples of the deposition gas containing silicon include silane,disilane, trisilane, and silane fluoride. As the oxidizing gas, oxygen,ozone, dinitrogen monoxide, and nitrogen dioxide can be given asexamples.

As the film formation conditions of the oxide insulating film 25, thehigh-frequency power having the above power density is supplied to atreatment chamber having the above pressure, whereby the degradationefficiency of the source gas in plasma is increased, oxygen radicals areincreased, and oxidation of the source gas is promoted; thus, the oxygencontent in the oxide insulating film 25 becomes higher than that in thestoichiometric composition. At the same time, in the film formed at asubstrate temperature within the above temperature range, the bondbetween silicon and oxygen is weak, and accordingly, part of oxygen inthe film is released by heat treatment in a later step. Thus, it ispossible to form an oxide insulating film which contains oxygen at ahigher proportion than oxygen in the stoichiometric composition and fromwhich part of oxygen is released by heating. Further, the oxideinsulating film 23 is provided over the oxide semiconductor film 17.Accordingly, in the step of forming the oxide insulating film 25, theoxide insulating film 23 serves as a protective film of the oxidesemiconductor film 17. Consequently, the oxide insulating film 25 can beformed using the high-frequency power having a high power density whiledamage to the oxide semiconductor film 17 is reduced. By the later heattreatment step, part of oxygen contained in the oxide insulating film 25can be moved to the oxide semiconductor film 17, so that the number ofoxygen vacancies contained in the oxide semiconductor film 17 can befurther reduced.

As the nitride insulating film 27, a film having an effect of blockingat least hydrogen and oxygen is used. Preferably, the nitride insulatingfilm 27 has an effect of blocking oxygen, hydrogen, water, an alkalimetal, an alkaline earth metal, or the like. It is possible to preventoutward diffusion of oxygen from the oxide semiconductor film 17 andentry of hydrogen, water, or the like into the oxide semiconductor film17 from the outside by providing the nitride insulating film 27.

The nitride insulating film 27 is formed using a silicon nitride film, asilicon nitride oxide film, an aluminum nitride film, an aluminumnitride oxide film, or the like having a thickness greater than or equalto 50 nm and less than or equal to 300 nm, preferably greater than orequal to 100 nm and less than or equal to 200 nm.

Note that instead of the nitride insulating film 27, an oxide insulatingfilm having a blocking effect against oxygen, hydrogen, water, and thelike may be provided. As the oxide insulating film having a blockingeffect against oxygen, hydrogen, water, and the like, an aluminum oxidefilm, an aluminum oxynitride film, a gallium oxide film, a galliumoxynitride film, an yttrium oxide film, an yttrium oxynitride film, ahafnium oxide film, and a hafnium oxynitride film can be given.

The nitride insulating film 27 can be formed by a sputtering method, aCVD method, or the like.

In the case where a silicon nitride film is formed by the plasma CVDmethod as the nitride insulating film 27, a deposition gas containingsilicon, nitrogen, and ammonia is used as the source gas. As the sourcegas, ammonia whose amount is smaller than the amount of nitrogen isused, whereby ammonia is dissociated in the plasma and activated speciesare generated. The activated species break a bond between silicon andhydrogen that are contained in a deposition gas containing silicon and atriple bond between nitrogen molecules. As a result, a dense siliconnitride film having a small number of defects, in which bonds betweensilicon and nitrogen are promoted and bonds between silicon and hydrogenis few, can be formed. In contrast, when the amount of ammonia is largerthan the amount of nitrogen in a source gas, dissociation of adeposition gas containing silicon and decomposition of nitrogen are notpromoted, so that a sparse silicon nitride film in which bonds betweensilicon and hydrogen remain and defects are increased is formed.Therefore, in a source gas, the flow ratio of the nitrogen to theammonia is set to be preferably greater than or equal to 5 and less thanor equal to 50, further preferably greater than or equal to 10 and lessthan or equal to 50.

In a transistor 10 b illustrated in FIG. 4B, the gate insulating film 15has a stacked structure of a nitride insulating film 29 and an oxideinsulating film 31 containing nitrogen, and the oxide insulating film 31in contact with the oxide semiconductor film 17 is an oxide insulatingfilm containing nitrogen and having a small number of defects.

As the nitride insulating film 29, a film having an effect of blockingwater, hydrogen, or the like is preferably used. Alternatively, as thenitride insulating film 29, a film having a small number of defects ispreferably used. Typical examples of the nitride insulating film 29include films of silicon nitride, silicon nitride oxide, aluminumnitride, aluminum nitride oxide, and the like.

The use of a silicon nitride film as the nitride insulating film 29 hasthe following effect. In addition, a silicon nitride film has a higherdielectric constant than a silicon oxide film and needs a largerthickness for capacitance equivalent to that of the silicon oxide. Thus,the physical thickness of the gate insulating film 15 can be increased.This makes it possible to reduce a decrease in withstand voltage of thetransistor 10 b and furthermore increase the withstand voltage, therebyreducing electrostatic discharge damage to a semiconductor device.

In the transistor including the oxide semiconductor film, when trapstates (also referred to as interface states) are included in the gateinsulating film 15, the trap states can cause a change in electricalcharacteristics, for a typical example, a change in the thresholdvoltage, of the transistor. As a result, there is a problem in thatelectrical characteristics vary among transistors. Therefore, with theuse of a silicon nitride film having a small number of defects as thenitride insulating film 29, the shift of the threshold voltage and thevariation in the electrical characteristics among transistors can bereduced.

The nitride insulating film 29 may have a stacked-layer structure. Forexample, the nitride insulating film 29 has a stacked structure in whicha first silicon nitride film is formed using a silicon nitride filmhaving a small number of defects, and a second silicon nitride filmusing a silicon nitride film that releases a small number of hydrogenmolecules and ammonia molecules is formed over the first silicon nitridefilm, whereby the gate insulating film 15 can be formed using a gateinsulating film that has a small number of defects and releases a smallnumber of hydrogen molecules and ammonia molecules. As a result,movement of hydrogen and nitrogen contained in the gate insulating film15 to the oxide semiconductor film 17 can be suppressed.

The nitride insulating film 29 is preferably formed by stacking siliconnitride films by a two-step formation method. First, a first siliconnitride film having a small number of defects is formed by a plasma CVDmethod in which a mixed gas of silane, nitrogen, and ammonia is used asa source gas. Then, by using a source gas at a flow ratio that issimilar to the above-described flow ratio of a source gas used for thenitride insulating film 27, a silicon nitride film that releases a smallnumber of hydrogen molecules and ammonia molecules can be formed as thesecond silicon nitride film.

<Modification Example 2>

Modification examples of the transistor 10 described in this embodimentare described with reference to FIGS. 5A and 5B. The transistor 10described in this embodiment is a channel-etched transistor; incontrast, a transistor 10 c described in this modification example is achannel-protective transistor.

The transistor 10 c illustrated in FIG. 5A includes the gate electrode13 over the substrate 11; the gate insulating film 15 over the substrate11 and the gate electrode 13; the oxide semiconductor film 17overlapping with the gate electrode 13 with the gate insulating film 15therebetween; an insulating film 33 over the gate insulating film 15 andthe oxide semiconductor film 17; and the pair of electrodes 19 and 20 incontact with the oxide semiconductor film 17 in openings of theinsulating film 33.

A transistor 10 d illustrated in FIG. 59 includes an insulating film 35over the oxide semiconductor film 17 and the pair of electrodes 19 and20 in contact with the oxide semiconductor film 17. End portions of thepair of electrodes 19 and 20 are formed over the insulating film 35.

In the transistor 10 c or 10 d, part of the oxide semiconductor film 17typified by a back channel region is covered with the insulating film 33or 35 when the pair of electrodes 19 and 20 are formed; accordingly, theback channel region of the oxide semiconductor film 17 is not damaged byetching for forming the pair of electrodes 19 and 20. In addition, whenthe insulating film 33 or 35 is an oxide insulating film containingnitrogen and having a small number of defects, a change in electricalcharacteristics is suppressed, whereby the transistor can have improvedreliability.

<Modification Example 3>

Modification examples of the transistor 10 described in this embodimentare described with reference to FIGS. 6A to 6C. The transistor 10described in this embodiment includes one gate electrode; in contrast, atransistor 10 e described in this modification example includes two gateelectrodes with an oxide semiconductor film interposed between the gateelectrodes.

A top view and cross-sectional views of the transistor 10 e included ina semiconductor device are illustrated in FIGS. 6A to 6C. FIG. 6A is atop view of the transistor 10 e, FIG. 6B is a cross-sectional view takenalong dashed-dotted line A-B in FIG. 6A, and FIG. CC is across-sectional view taken along dashed-dotted line C-D in FIG. 6A. Notethat in FIG. 6A, the substrate 11, the gate insulating film 15, theprotective film 21, and the like are omitted for simplicity.

The transistor 10 e illustrated in FIGS. 6B and 6C is a channel-etchedtransistor including the gate electrode 13 over the substrate 11; thegate insulating film 15 formed over the substrate 11 and the gateelectrode 13; the oxide semiconductor film 17 overlapping with the gateelectrode 13 with the gate insulating film 15 provided therebetween; andthe pair of electrodes 19 and 20 in contact with the oxide semiconductorfilm 17. The transistor 10 e further includes the protective film 21including the oxide insulating film 23, the oxide insulating film 25,and the nitride insulating film 27 over the gate insulating film 15, theoxide semiconductor film 17, and the pair of electrodes 19 and 20; and agate electrode 37 formed over the protective film 21. The gate electrode37 is connected to the gate electrode 13 through openings 42 and 43provided in the gate insulating film 15 and the protective film 21.Here, the gate insulating film 15 is a stack of the nitride insulatingfilm 29 and oxide insulating film 31. The protective film 21 is a stackof the oxide insulating film 23, the oxide insulating film 25, and thenitride insulating film 27.

A plurality of openings are provided in the gate insulating film 15 andthe protective film 21. As a typical example, the openings 42 and 43 areprovided with the oxide semiconductor film 17 provided therebetween inthe channel width direction as illustrated in FIG. 6C. In other words,the openings 42 and 43 are provided on outer sides of the side surfacesof the oxide semiconductor film 17. In addition, in the openings 42 and43, the gate electrode 13 is connected to the gate electrode 37. Thismeans that the gate electrode 13 and the gate electrode 37 surround theoxide semiconductor film 17 in the channel width direction with the gateinsulating film 15 and the protective film 21 provided between the oxidesemiconductor film 17 and each of the gate electrode 13 and the gateelectrode 37. Furthermore, in the channel width direction, the gateelectrode 37 in the openings 42 and 43 and each of the side surfaces ofthe oxide semiconductor film 17 are provided so that the protective film21 is positioned therebetween.

As illustrated in FIG. 6C, a side surface of the oxide semiconductorfilm 17 faces the gate electrode 37 in the channel width direction, andthe oxide semiconductor film 17 is surrounded by the gate electrode 13and the gate electrode 37 with the gate insulating film 15 interposedbetween the oxide semiconductor film 17 and the gate electrode 13 andthe protective film 21 interposed between the oxide semiconductor film17 and the gate electrode 37 in the channel width direction. Thus, inthe oxide semiconductor film 17, carriers flow not only at the interfacebetween the gate insulating film 15 and the oxide semiconductor film 17and the interface between the protective film 21 and the oxidesemiconductor film 17, but also in the oxide semiconductor film 17,whereby the amount of transfer of carriers is increased in thetransistor 10 e. As a result, the on-state current and field-effectmobility of the transistor 10 are increased. The electric field of thegate electrode 37 affects the side surface or an end portion includingthe side surface and its vicinity of the oxide semiconductor film 17;thus, generation of a parasitic channel at the side surface or the endportion of the oxide semiconductor film 17 can be suppressed.

<Modification Example 4>

Modification examples of the transistor 10 described in this embodimentare described with reference to FIGS. 7A to 7F and FIGS. 8A to 8C. Thetransistor 10 described in this embodiment includes the single-layeroxide semiconductor film; in contrast, transistors 10 f and 10 gdescribed in this modification example each includes a multi-layer film.

FIGS. 7A to 7C are a top view and cross-sectional views of thetransistor 10 f included in a semiconductor device. FIG. 7A is a topview of the transistor 10 f, FIG. 7B is a cross-sectional view takenalong dashed-dotted line A-B in FIG. 7A, and FIG. 7C is across-sectional view taken along dashed-dotted line C-D in FIG. 7A. Notethat in FIG. 7A, the substrate 11, the gate insulating film 15, theprotective film 21, and the like are omitted for simplicity.

The transistor 10 f illustrated in FIG. 7A includes a multilayer film 45overlapping with the gate electrode 13 with the gate insulating film 15provided therebetween, and the pair of electrodes 19 and 20 in contactwith the multilayer film 45. The protective film 21 is stacked over thegate insulating film 15, the multilayer film 45, and the pair ofelectrodes 19 and 20.

In the transistor 10 f described in this embodiment, the multilayer film45 includes the oxide semiconductor film 17 and an oxide semiconductorfilm 46. That is, the multilayer film 45 has a two-layer structure.Furthermore, part of the oxide semiconductor film 17 serves as a channelregion. In addition, the protective film 21 is formed in contact withthe multilayer film 45.

The oxide semiconductor film 46 contains one or more elements that formthe oxide semiconductor film 17. Thus, interface scattering is unlikelyto occur at the interface between the oxide semiconductor film 17 andthe oxide semiconductor film 46. Thus, the transistor can have highfield-effect mobility because the movement of carriers is not hinderedat the interfaces.

The oxide semiconductor film 46 is formed using a metal oxide filmcontaining at least In or Zn. Typical examples of the metal oxide filminclude an In—Ga oxide film, an In—Zn oxide film, and an In—M—Zn oxidefilm (M represents Al, Ga, Y, Zr, La, Ce, or Nd). The conduction bandminimum of the oxide semiconductor film 46 is closer to a vacuum levelthan that of the oxide semiconductor film 17 is; as a typical example,the energy difference between the conduction band minimum of the oxidesemiconductor film 46 and the conduction band minimum of the oxidesemiconductor film 17 is any one of 0.05 eV or more, 0.07 eV or more,0.1 eV or more, or 0.15 eV or more, and any one of 2 eV or less, 1 eV orless, 0.5 eV or less, or 0.4 eV or less. That is, the difference betweenthe electron affinity of the oxide semiconductor film 46 and theelectron affinity of the oxide semiconductor film 17 is any one of 0.05eV or more, 0.07 eV or more, 0.1 eV or more, or 0.15 eV or more, and anyone of 2 eV or less, 1 eV or less, 0.5 eV or less, or 0.4 eV or less.

The oxide semiconductor film 46 preferably contains In because carriermobility (electron mobility) can be increased.

When the oxide semiconductor film 46 contains a larger amount of Al, Ga,Y, Zr, La, Ce, or Nd than the amount of In in an atomic ratio, any ofthe following effects may be obtained: (1) the energy gap of the oxidesemiconductor film 46 is widened; (2) the electron affinity of the oxidesemiconductor film 46 decreases; (3) impurity diffusion from the outsideis suppressed; (4) an insulating property of the oxide semiconductorfilm 46 increases as compared to that of the oxide semiconductor film17; and (5) an oxygen vacancy is less likely to be generated because Al,Ga, Y, Zr, La, Ce, or Nd is a metal element that is strongly bonded tooxygen.

In the case where the oxide semiconductor film 46 is formed of anIn—M—Zn oxide, the proportions of In and M when summation of In and M isassumed to be 100 atomic % are preferably as follows: the proportion ofIn is less than 50 atomic % and the proportion of M is greater than 50atomic %, or further preferably, the proportion of In is less than 25atomic % and the proportion of M is greater than 75 atomic %.

Furthermore, in the case where each of the oxide semiconductor films 17and 46 contains an In—M—Zn oxide (M represents Al, Ga, Y, Zr, La, Ce, orNd), the proportion of M atoms (M represents Al, Ga, Y, Zr, La, Ce, orNd) in the oxide semiconductor film 46 is higher than that in the oxidesemiconductor film 17. As a typical example, the proportion of M in theoxide semiconductor film 17 is 1.5 or more times, preferably twice ormore, further preferably three or more times as high as that in theoxide semiconductor film 17.

Furthermore, in the case where each of the oxide semiconductor films 17and 46 contains an In—M—Zn oxide (M represents Al, Ga, Y, Zr, La, Ce, orNd), when In:M:Zn=x₁:y₁:z₁ [atomic ratio] is satisfied in the oxidesemiconductor film 46 and In:M:Zn=x₂:y₂:z₂ [atomic ratio] is satisfiedin the oxide semiconductor film 17, y₁/x₁ is higher than y₂/x₂, andpreferably, y₁/x₁ be 1.5 or more times as high as y₂/x₂. Alternatively,y₁/x₁ is preferably twice or more as high as y₂/x₂. Furtheralternatively, y₁/x₁ is preferably three or more times as high as y₂/x₂.In this case, it is preferable that in the oxide semiconductor film, y₂be higher than or equal to x₂ because a transistor including the oxidesemiconductor film can have stable electrical characteristics.

In the case where the oxide semiconductor film 17 is an In—M—Zn oxidefilm (M is Al, Ga, Y, Zr, La, Ce, or Nd) and a target having the atomicratio of metal elements of In:M:Zn=x₁:y₁:z₁ is used for forming theoxide semiconductor film 17, x₁/y₁ is preferably greater than or equalto ⅓ and less than or equal to 6, further preferably greater than orequal to 1 and less than or equal to 6, and z₁/y₁ is preferably greaterthan or equal to ⅓ and less than or equal to 6, further preferablygreater than or equal to 1 and less than or equal to 6. Note that whenz₁/y₁ is greater than or equal to 1 and less than or equal to 6, aCAAC-OS film to be described later as the oxide semiconductor film 17 iseasily formed. Typical examples of the atomic ratio of the metalelements of the target are In:M:Zn=1:1:1, In:M:Zn=1:1:1.2, andIn:M:Zn=3:1:2.

In the case where the oxide semiconductor film 46 is an In—M—Zn oxidefilm (M is Al, Ga, Y, Zr, La, Ce, or Nd) and a target having the atomicratio of metal elements of In:M:Zn=x₂:y₂:z₂ is used for forming theoxide semiconductor film 46, x₂/y₂ is preferably less than x₁/y₁, andz₂/y₂ is preferably greater than or equal to ⅓ and less than or equal to6, further preferably greater than or equal to 1 and less than or equalto 6. Note that when z₂/y₂ is greater than or equal to 1 and less thanor equal to 6, a CAAC-OS film to be described later as the oxidesemiconductor film 46 is easily formed. Typical examples of the atomicratio of the metal elements of the target are In:M:Zn=1:3:2,In:M:Zn=1:3:4, In:M:Zn=1:3:6, In:M:Zn=1:3:8, In:M:Zn=1:4:3,In:M:Zn=1:4:4, In:M:Zn=1:4:5, In:M:Zn=1:4:6, In:M:Zn=1:5:5,In:M:Zn=1:5:6, and the like.

Note that the proportion of each metal element in the atomic ratio ofeach of the oxide semiconductor films 17 and 46 varies within a range of±40% of that in the above atomic ratio as an error.

The thickness of the oxide semiconductor film 46 is greater than orequal to 3 nm and less than or equal to 100 nm, preferably greater thanor equal to 3 nm and less than or equal to 50 nm.

The oxide semiconductor film 46 may have a non-single-crystal structure,for example, like the oxide semiconductor film 17. The non-singlecrystal structure includes a c-axis aligned crystalline oxidesemiconductor (CAAC-OS) that is described later, a polycrystallinestructure, a microcrystalline structure described later, or an amorphousstructure, for example.

The oxide semiconductor film 46 may have an amorphous structure, forexample. An amorphous oxide semiconductor film has, for example,disordered atomic arrangement and no crystalline component.Alternatively, an amorphous oxide semiconductor film has, for example,an absolutely amorphous structure and no crystal part.

Note that the oxide semiconductor films 17 and 46 may each be a mixedfilm including two or more of a region having an amorphous structure, aregion having a microcrystalline structure, a region having apolycrystalline structure, a CAAC-OS region, and a region having asingle-crystal structure. The mixed film has a single-layer structureincluding, for example, two or more of a region having an amorphousstructure, a region having a microcrystalline structure, a region havinga polycrystalline structure, a CAAC-OS region, and a region having asingle-crystal structure in some cases. Furthermore, in some cases, themixed film has a stacked-layer structure of two or more of a regionhaving an amorphous structure, a region having a microcrystallinestructure, a region having a polycrystalline structure, a CAAC-OSregion, and a region having a single-crystal structure.

In this case, the oxide semiconductor film 46 is provided between theoxide semiconductor film 17 and the protective film 21. Thus, if carriertraps are formed between the oxide semiconductor film 46 and theprotective film 21 by impurities and defects, electrons flowing in theoxide semiconductor film 17 are less likely to be trapped by the carriertraps because there is a distance between the region where the carriertraps are formed and the oxide semiconductor film 17. Accordingly, theamount of on-state current of the transistor can be increased, and thefield-effect mobility can be increased. When the electrons are trappedby the carrier traps, the electrons become negative fixed charges. As aresult, the threshold voltage of the transistor varies. However, by thedistance between the region where the carrier traps are formed and theoxide semiconductor film 17, trap of the electrons by the carrier trapscan be reduced, and accordingly fluctuations of the threshold voltagecan be reduced.

The oxide semiconductor film 46 can block impurities from the outside,and accordingly, the amount of impurities that are transferred from theoutside to the oxide semiconductor film 17 can be reduced. Furthermore,an oxygen vacancy is less likely to be formed in the oxide semiconductorfilm 46. Consequently, the impurity concentration and the number ofoxygen vacancies in the oxide semiconductor film 17 can be reduced.

Note that the oxide semiconductor films 17 and 46 are not formed bysimply stacking each film, but are formed to form a continuous junction(here, in particular, a structure in which the energy of the conductionband minimum is changed continuously between each film). In other words,a stacked-layer structure in which there exists no impurity that forms adefect level such as a trap center or a recombination center at eachinterface is provided. If an impurity exists between the oxidesemiconductor films 17 and 46 that are stacked, a continuity of theenergy band is damaged, and the carrier is trapped or recombined at theinterface and then disappears.

To form such a continuous energy band, it is necessary to form filmscontinuously without being exposed to the air, with use of amulti-chamber deposition apparatus (sputtering apparatus) including aload lock chamber. Each chamber in the sputtering apparatus ispreferably evacuated to be a high vacuum state (to the degree of about5×10⁻⁷ Pa to 1×10⁻⁴ Pa) with an adsorption vacuum evacuation pump suchas a cryopump in order to remove water or the like, which serves as animpurity against the oxide semiconductor film, as much as possible.Alternatively, a turbo molecular pump and a cold trap are preferablycombined so as to prevent a backflow of gas, especially gas containingcarbon or hydrogen from an exhaust system to the inside of the chamber.

Note that a multilayer film 48 in the transistor 10 g illustrated inFIG. 7D may be included instead of the multilayer film 45.

An oxide semiconductor film 47, the oxide semiconductor film 17, and theoxide semiconductor film 46 are stacked in this order in the multilayerfilm 48. That is, the multilayer film 48 has a three-layer structure.Furthermore, the oxide semiconductor film 17 serves as a channel region.

The gate insulating film 15 is in contact with the oxide semiconductorfilm 47.

In other words, the oxide semiconductor film 47 is provided between thegate insulating film 15 and the oxide semiconductor film 17.

Furthermore, e oxide semiconductor film 46 is in contact with theprotective film 21. That is, the oxide semiconductor film 46 is providedbetween the oxide semiconductor film 17 and the protective film 21.

The oxide semiconductor film 47 can be formed using a material and aformation method similar to those of the oxide semiconductor film 46.

It is preferable that the thickness of the oxide semiconductor film 47be smaller than that of the oxide semiconductor film 17. When thethickness of the oxide semiconductor film 47 is greater than or equal to1 nm and less than or equal to 5 nm, preferably greater than or equal to1 nm and less than or equal to 3 nm, the amount of change in thethreshold voltage of the transistor can be reduced.

In the transistors described in this embodiment, the oxide semiconductorfilm 46 is provided between the oxide semiconductor film 17 and theprotective film 21. Thus, if carrier traps are formed between the oxidesemiconductor film 46 and the protective film 21 by impurities anddefects, electrons flowing in the oxide semiconductor film 17 are lesslikely to be trapped by the carrier traps because there is a distancebetween the region where the carrier traps are formed and the oxidesemiconductor film 17. Accordingly, the amount of on-state current ofthe transistor can be increased, and the field-effect mobility can beincreased. When the electrons are trapped by the carrier traps, theelectrons behave as negative fixed charges. As a result, the thresholdvoltage of the transistor varies. However, by the distance between theregion where the carrier traps are formed and the oxide semiconductorfilm 17, trap of electrons by the carrier traps can be reduced, andaccordingly, fluctuations of the threshold voltage can be reduced.

The oxide semiconductor film 46 can block entry of impurities from theoutside, and accordingly, the amount of impurities transferred to theoxide semiconductor film 17 from the outside can be reduced.Furthermore, an oxygen vacancy is less likely to be formed in the oxidesemiconductor film 46. Consequently, the impurity concentration and thenumber of oxygen vacancies in the oxide semiconductor film 17 can bereduced.

The oxide semiconductor film 47 is provided between the gate insulatingfilm 15 and the oxide semiconductor film 17, and the oxide semiconductorfilm 46 is provided between the oxide semiconductor film 17 and theprotective film 21. Thus, it is possible to reduce the concentration ofsilicon or carbon in the vicinity of the interface between the oxidesemiconductor film 47 and the oxide semiconductor film 17, in the oxidesemiconductor film 17, or in the vicinity of the interface between theoxide semiconductor film 46 and the oxide semiconductor film 17.

The transistor 10 g having such a structure includes very few defects inthe multilayer film 48 including the oxide semiconductor film 17; thus,the electrical characteristics, typified by the on-state current and thefield-effect mobility, of these transistors can be improved. Further, ina gate BT stress test and a gate BT photostress test that are examplesof a stress test, the amount of change in threshold voltage is small,and thus, reliability is high.

The transistor 10 f illustrated in FIG. 7B can be provided with the gateelectrode 37 so that a transistor 10 h can be manufactured (see FIG.7E). The transistor 10 g illustrated in FIG. 7D can be provide with thegate electrode 37 so that a transistor 10 i can be manufactured (seeFIG. 7F).

<Band Structure of Transistor>

Next, band structures of the multilayer film 45 included in thetransistor 10 f illustrated in FIG. 7A and the multilayer film 48included in the transistor 10 g illustrated in FIG. 7D are describedwith reference to FIGS. 8A to 8C.

Here, for example, an In—Ga—Zn oxide having an energy gap of 3.15 eV isused for the oxide semiconductor film 17, and an In—Ga—Zn oxide havingan energy gap of 3.5 eV is used for the oxide semiconductor film 46. Theenergy gaps can be measured using a spectroscopic ellipsometer (UT-300manufactured by HORIBA JOBIN YVON SAS.).

The energy difference between the vacuum level and the valence bandmaximum (also called ionization potential) of the oxide semiconductorfilm 17 and the energy difference between the vacuum level and thevalence band maximum of the oxide semiconductor film 46 are 8 eV and 8.2eV, respectively. Note that the energy difference between the vacuumlevel and the valence band maximum can be measured using an ultravioletphotoelectron spectroscopy (UPS) device (VersaProbe manufactured byULVAC-PHI, Inc.).

Thus, the energy difference between the vacuum level and the conductionband minimum (also called electron affinity) of the oxide semiconductorfilm 17 and the energy difference between the vacuum level and theconduction band minimum of the oxide semiconductor film 46 are 4.85 eVand 4.7 eV, respectively.

FIG. 8A schematically illustrates a part of the band structure of themultilayer film 45 included in the transistor 10 f. Here, the case wheresilicon oxide films are used for the gate insulating film 15 and theprotective film 21 and the silicon oxide films are provided in contactwith the multilayer film 45 is described. In FIG. 8A, EcI1 denotes theenergy of the conduction band minimum of the silicon oxide film; EcS1denotes the energy of the conduction band minimum of the oxidesemiconductor film 17; EcS2 denotes the energy of the conduction bandminimum of the oxide semiconductor film 46; and EcI2 denotes the energyof the conduction band minimum of the silicon oxide film. Furthermore,EcI1 and EcI2 correspond to the gate insulating film 15 and theprotective film 21 in FIG. 7B, respectively.

As illustrated in FIG. 8A, there is no energy barrier between the oxidesemiconductor films 17 and 46, and the energy of the conduction bandminimum gradually changes therebetween. In other words, the energy ofthe conduction band minimum is continuously changed. This is because themultilayer film 45 contains an element contained in the oxidesemiconductor film 17 and oxygen is transferred between the oxidesemiconductor films 17 and 46, so that a mixed layer is formed.

As shown in FIG. 8A, the oxide semiconductor film 17 in the multilayerfilm 45 serves as a well and a channel region of the transistorincluding the multilayer film 45 is formed in the oxide semiconductorfilm 17. Note that since the energy of the conduction band minimum ofthe multilayer film 45 is continuously changed, it can be said that theoxide semiconductor films 17 and 46 are continuous.

Although trap levels due to impurities or defects might be generated inthe vicinity of the interface between the oxide semiconductor film 46and the protective film 21 as shown in FIG. 8A, the oxide semiconductorfilm 17 can be distanced from the region where the trap levels aregenerated owing to the existence of the oxide semiconductor film 46.However, when the energy difference between EcS1 and EcS2 is small, anelectron in the oxide semiconductor film 17 might reach the trap levelacross the energy difference. When the electron is trapped by the traplevel, a negative fixed charge is generated at the interface with theoxide insulating film, whereby the threshold voltage of the transistorshifts in the positive direction. Thus, it is preferable that the energydifference between EcS1 and EcS2 be 0.1 eV or more, further preferably0.15 eV or more, because a change in the threshold voltage of thetransistor is reduced and stable electrical characteristics areobtained.

FIG. 8B schematically illustrates a part of the band structure of themultilayer film 45 of the transistor 10 f, which is a variation of theband structure shown in FIG. 8A. Here, a structure where silicon oxidefilms are used for the gate insulating film 15 and the protective film21 and the silicon oxide films are in contact with the multilayer film45 is described. In FIG. 8B, EcI1 denotes the energy of the conductionband minimum of the silicon oxide film; EcS1 denotes the energy of theconduction band minimum of the oxide semiconductor film 17; and EcI2denotes the energy of the conduction band minimum of the silicon oxidefilm. Further, EcI1 and EcI2 correspond to the gate insulating film 15and the protective film 21 in FIG. 7B, respectively.

In the transistor illustrated in FIG. 7B, an upper portion of themultilayer film 45, that is, the oxide semiconductor film 46 might beetched in formation of the pair of electrodes 19 and 20. Furthermore, amixed layer of the oxide semiconductor films 17 and 46 is likely to beformed on the top surface of the oxide semiconductor film 17 information of the oxide semiconductor film 46.

For example, Ga content in the oxide semiconductor film 46 is higherthan that in the oxide semiconductor film 17 in the case where the oxidesemiconductor film 17 is an oxide semiconductor film formed with use of,as a sputtering target, In—Ga—Zn oxide whose atomic ratio of In to Gaand Zn is 1:1:1 or In—Ga—Zn oxide whose atomic ratio of In to Ga and Znis 3:1:2, and the oxide semiconductor film 46 is an oxide film formedwith use of, as a sputtering target, In—Ga—Zn oxide whose atomic ratioof In to Ga and Zn is 1:3:2, In—Ga—Zn oxide whose atomic ratio of In toGa and Zn is 1:3:4, or In—Ga—Zn oxide whose atomic ratio of In to Ga andZn is 1:3:6. Thus, a GaO_(x) layer or a mixed layer whose Ga content ishigher than that in the oxide semiconductor film 17 can be formed on thetop surface of the oxide semiconductor film 17.

For that reason, even in the case where the oxide semiconductor film 46is etched, the energy of the conduction band minimum EcS1 on the EcI2side is increased, and the band structure shown in FIG. 8B can beobtained in some cases.

As in the band structure shown in FIG. 8B, in observation of a crosssection of a channel region, only the oxide semiconductor film 17 in themultilayer film 45 is apparently observed in some cases. However, amixed layer that contains Ga more than the oxide semiconductor film 17is formed over the oxide semiconductor film 17 in fact, and thus themixed layer can be regarded as a 1.5-th layer. Note that the mixed layercan be confirmed by analyzing a composition in the upper portion of theoxide semiconductor film 17, when the elements contained in themultilayer film 45 are measured by an EDX analysis, for example. Themixed layer can be confirmed, for example, in such a manner that the Gacontent in the composition in the upper portion of the oxidesemiconductor film 17 is larger than the Ga content in the oxidesemiconductor film 17.

FIG. 8C schematically illustrates a part of the band structure of themultilayer film 48 of the transistor 10 g. Here, the case where siliconoxide films are used for the gate insulating film 15 and the protectivefilm 21 and the silicon oxide films are in contact with the multilayerfilm 48 is described. In FIG. 8C, EcI1 denotes the energy of theconduction band minimum of the silicon oxide film; EcS1 denotes theenergy of the conduction band minimum of the oxide semiconductor film17; EcS2 denotes the energy of the conduction band minimum of the oxidesemiconductor film 46; EcS3 denotes the energy of the conduction bandminimum of the oxide semiconductor film 47; and EcI2 denotes the energyof the conduction band minimum of the silicon oxide film. Furthermore,EcI1 and EcI2 correspond to the gate insulating film 15 and theprotective film 21 in FIG. 7D, respectively.

As illustrated in FIG. 8C, there is no energy barrier between the oxidesemiconductor films 47, 17, and 46, and the conduction band minimumsthereof smoothly vary. In other words, the conduction band minimums arecontinuous. This is because the multilayer film 48 contains an elementcontained in the oxide semiconductor film 17 and oxygen is transferredbetween the oxide semiconductor films 17 and 47 and between the oxidesemiconductor films 17 and 46, so that a mixed layer is formed.

As shown in FIG. 8C, the oxide semiconductor film 17 in the multilayerfilm 48 serves as a well and a channel region of the transistorincluding the multilayer film 48 is formed in the oxide semiconductorfilm 17. Note that since the energy of the conduction band minimum ofthe multilayer film 48 is continuously changed, it can be said that theoxide semiconductor films 47, 17, and 46 are continuous.

Although trap levels due to impurities or defects might be generated inthe vicinity of the interface between the oxide semiconductor film 17and the protective film 21 and in the vicinity of the interface betweenthe oxide semiconductor film 17 and the gate insulating film 15, asillustrated in FIG. 8C, the oxide semiconductor film 17 can be distancedfrom the region where the trap levels are generated owing to theexistence of the oxide semiconductor films 46 and 47. However, when theenergy difference between EcS1 and EcS2 and the energy differencebetween EcS1 and EcS3 are small, electrons in the oxide semiconductorfilm 17 might reach the trap level across the energy difference. Whenthe electrons are trapped by the trap level, a negative fixed charge isgenerated at the interface with the insulating film, whereby thethreshold voltage of the transistor shifts in the positive direction.Thus, it is preferable that the energy difference between EcS1 and EcS2and the energy difference between EcS1 and EcS3 be 0.1 eV or more,further preferably 0.15 eV or more, because a change in the thresholdvoltage of the transistor is reduced and stable electricalcharacteristics are obtained.

Instead of the oxide semiconductor film 46, a metal oxide film formed ofan In-M oxide (M is Al, Ga, Y, Zr, La, Ce, or Nd) can be used. Note thatto prevent the metal oxide film from functioning as part of a channelregion, a material having sufficiently low conductivity is used for themetal oxide film. Alternatively, a material which has a smaller electronaffinity (an energy difference between a vacuum level and a conductionband minimum) than the oxide semiconductor film 17 and has a differencein conduction band minimum from the oxide semiconductor film 17 (bandoffset) is used for the metal oxide film. Furthermore, to inhibitgeneration of a difference between threshold voltages due to the valueof the drain voltage, it is preferable to use a metal oxide film whoseconduction band minimum is closer to the vacuum level than theconduction band minimum of the oxide semiconductor film 17 is by 0.2 eVor more, preferably 0.5 eV or more.

When an atomic ratio of M to In (M/In) is increased, the energy gap ofthe metal oxide film is increased and the electron affinity thereof canbe small. In the case where a material containing an In-M oxide (M isAl, Ga, Y, Zr, La, Ce, or Nd) is used for the metal oxide film, forexample, and where the atomic ratio of In to Al in the metal oxide filmis x:y, y/(x+y) is preferably greater than or equal to 0.75 and lessthan or equal to 1, further preferably greater than or equal to 0.78 andless than or equal to 1, still further preferably greater than or equalto 0.80 and less than or equal to 1 in order to form a conduction bandoffset between the metal oxide film and the oxide semiconductor film 17and inhibit a channel from being formed in the metal oxide film. Notethat an element other than indium, M, and oxygen that are maincomponents may be mixed in the metal oxide film as an impurity. In thatcase, the impurity preferably accounts for less than or equal to 0.1% ofthe metal oxide film.

In the case where the metal oxide film is formed by a sputtering method,when the atomic ratio of the element Al to In is increased, the numberof particles in deposition can be reduced. To reduce the number ofparticles, when the atomic ratio is In:M=x:y, y/(x+y) may be greaterthan or equal to 0.90, e.g., 0.93. Note that in the case where the metaloxide film is formed by a sputtering method, when the atomic ratio of Mto In is too high, the insulating property of a target becomes high,which makes it difficult to perform deposition using DC discharge; as aresult, it is necessary to use RF discharge. Accordingly, whendeposition is performed using DC discharge, which is applicable to thecase of using a large-sized substrate, y/(x+y) is set less than or equalto 0.96, preferably less than or equal to 0.95, e.g., 0.93. The use ofthe deposition method applicable to the case of using a large-sizedsubstrate can increase the productivity of the semiconductor device.

Note that it is preferable that the metal oxide film not have a spinelcrystal structure. This is because if the metal oxide film has a spinelcrystal structure, a constituent element of the pair of electrodes 19and 20 might be diffused into the oxide semiconductor film 17 throughthe region between the spinel crystal structure and another region. Forexample, it is preferable that an In-M oxide be used as the metal oxidefilm and that a divalent metal element (e.g., zinc) not be contained asM, in which case the formed metal oxide film does not have a spinelcrystal structure.

The thickness of the metal oxide film is greater than or equal to athickness that is capable of inhibiting diffusion of the constituentelement of the pair of electrodes 19 and 20 into the oxide semiconductorfilm 17, and less than a thickness which inhibits supply of oxygen fromthe protective film 21 to the oxide semiconductor film 17. For example,when the thickness of the metal oxide film is greater than or equal to10 nm, the constituent element of the pair of electrodes 19 and 20 canbe prevented from diffusing into the oxide semiconductor film 17. Whenthe thickness of the metal oxide film is less than or equal to 100 nm,oxygen can be effectively supplied from the protective film 21 to theoxide semiconductor film 17.

<Modification Example 5>

A modification example of the transistor described in this embodiment isdescribed with reference to FIGS. 10A to 10C. A transistor 10 jdescribed in this modification example includes an oxide semiconductorfilm 17 a and a pair of electrodes 19 a and 20 a that are formed using amulti-tone mask.

With the use of the multi-tone mask, a resist mask having pluralthicknesses can be formed. After the oxide semiconductor film 17 a isformed using the resist mask, the resist mask is exposed to oxygenplasma or the like; thus, the resist mask is partly removed to be aresist mask used for forming the pair of electrodes. As a result, thenumber of steps in photolithography in a process for forming the oxidesemiconductor film 17 a and the pair of electrodes 19 a and 20 a can bereduced.

With the use of a multi-tone mask, the oxide semiconductor film 17 a ispartly exposed to the outside of the pair of electrodes 19 a and 20 awhen seen from the above.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

<Modification Example 6>

Modification examples of the transistor described in this embodiment aredescribed with reference to FIG. 9. A transistor 10 k described in thismodification example includes an organic insulating film 38 over theprotective film 21.

As the organic insulating film 38, an organic resin film of polyimide,acrylic, polyamide, epoxy, or the like can be used, for example. Theorganic insulating film 38 preferably has a thickness greater than orequal to 500 nm and less than or equal to 10 μm.

The organic insulating film 38 may be provided to cover the wholeprotective film 21. Alternatively, the organic insulating film 38 may beprovided for each transistor to overlap with the oxide semiconductorfilm 17 of each transistor. The organic insulating film 38 is preferablyisolated from other organic insulating film 38 because water from theoutside is not diffused into a semiconductor device through the organicinsulating film 38.

Since the organic insulating film 38 is thick (greater than or equal to500 nm), an electric field generated by application of negative voltageto the gate electrode 13 does not affect a surface of the organicinsulating film 38; as a result, positive charges are less likely to beaccumulated on the surface of the organic insulating film 38. Inaddition, even when positively charged particle in the air is adsorbedon the surface of the organic insulating film 38, the electric field ofthe positively charged particle adsorbed on the surface of the organicinsulating film 38 is less likely to affect the interface between theoxide semiconductor film 17 and the protective film 21, because theorganic insulating film 38 is thick (greater than or equal to 500 nm).As a result, practically no positive bias is applied to the interfacebetween the oxide semiconductor film 17 and the protective film 21;thus, a change in the threshold voltage of the transistor is small.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

(Embodiment 2)

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

<1. NO_(x)>

First, nitrogen oxide (hereinafter NO_(x); x is greater than or equal to0 and less than or equal to 2, preferably greater than or equal to 1 andless than or equal to 2) contained in the oxide insulating film incontact with the oxide semiconductor film is described.

<1-1. Transition Level of NO_(x) in Oxide Insulating Film>

First, transition levels of point defects in a solid are described. Atransition level shows the charge state of impurities or defects(hereinafter referred to as a defect D) forming a state in a gap, and iscalculated from the formation energy of defects. In other words, atransition level is similar to a donor level or an acceptor level.

The relationship between formation energy and transition levels of thecharge state of the defect D and is described. The formation energy ofthe defect D is different depending on the charge state and also dependson the Fermi energy. Note that D⁺ represents a state in which a defectreleases one electron, D⁻ represents a state in which a defect traps oneelectron, and D⁰ represents a state in which no electron is transferred.

FIG. 11A illustrates the relationship between the formation energy andthe transition level of each of the defects D⁺, D⁰, and D⁻. FIG. 11Billustrates electron configurations of the detects D⁺, D⁰, and D⁻ in thecase where the defect D in a neutral state has an orbit occupied by oneelectron.

In FIG. 11A, the dotted line indicates the formation energy of thedefect D⁺, the solid line indicates the formation energy of the defectD⁰, and the dashed line indicates the formation energy of the detect D⁻.The transition level means the position of the Fermi level at which theformation energies of the defects D having different charge statesbecome equal to each other. The position of the Fermi level at which theformation energy of the defect D⁺ becomes equal to that of the defect D⁰(that is, a position at which the dotted line and the solid lineintersect) is denoted by ε(+/0), and the position of the Fermi level atwhich the formation energy of the defect D⁰ becomes equal to that of thedefect D⁻ (that is, a position at which the solid line and the dashedline intersect) is denoted by ε(0/−).

FIG. 12 illustrates a conceptual diagram of transition of charge statesof a defect that are energetically stable when the Fermi level ischanged. In FIG, 12, the dashed double-dotted line indicates the Fermilevel. Right views of FIG. 12 are band diagrams of (1), (2), and (3)that indicate the Fermi level in a left view of FIG. 12.

By finding out the transition level of a solid, it is qualitativelyknown that which charge state allows a detect to be energetically stableat each of the Fermi levels when the Fermi level is used as a parameter.

As a typical example of the oxide insulating film in contact with theoxide semiconductor film, a silicon oxynitride (SiON) film was used, andthe defect level in the silicon oxynitride film and an ESR signalattributed to the defect level were examined by calculation.Specifically, models in which NO₂, N₂O, NO, and an N atom wereintroduced into the respective silicon oxide (SiO₂) were formed, and thetransition levels thereof were examined to verify whether NO₂, N₂O, NO,and an N atom introduced into silicon oxide serve as electron traps ofthe transistor.

In calculation, SiO₂(c-SiO₂) with a low-temperature quartz (α-quartz)crystal structure was used as a model. A crystal model of c-SiO₂ withoutdefects is shown in FIG. 13.

First, structure optimization calculation was performed on a modelincluding 72 atoms, particularly on the lattice constants and the atomiccoordinates. The model was obtained by doubling the unit cells in allaxis direction of c-SiO₂. In the calculation, first principlescalculation software VASP (the Vienna Ab initio Simulation Package) wasused. The effect of inner-shell electron was calculated by a projectoraugmented wave (PAW) method, and as a functional, Heyd-Scuseria-Emzerhof(HSE) DFT hybrid factor (HSE06) was used. The calculation conditions areshown below.

TABLE 1 Software VASP Pseudopotential PAW method Functional HSE06 Mixingratio of 0.4 exchange term Cut-off energy 800 eV k-point 1 × 1 × 1optimization  2 × 2 × 2 (total energy)

The band gap of c-SiO₂ model after the structure optimization was 8.97eV that is close to the experimental value, 9.0 eV.

Next, the structure optimization calculation was performed on the abovec-SiO₂ models where NO₂, N₂O, NO, and an N atom were introduced intospaces (interstitial sites) in respective crystal structures. Thestructure optimization calculation was performed on each model withrespect to the following three cases: a case where the whole model ispositive monovalent (charge: +1); a case where the whole model iselectrically neutral (zerovalent) (charge: neutral); and a case wherethe whole model is negative monovalent (charge: −1). Note that thecharges imposed on the whole model, which were in the ground state ofelectrons, were localized in defects including NO₂, N₂O, NO, and an Natom.

As for the model in which NO₂ was introduced into an interstitial sitein the c-SiO₂ model, a structure after the structure optimizationcalculation was performed and structural parameters of an NO₂ are shownin FIG. 14. In FIG. 14, structural parameters of an NO₂ molecule in agaseous state are also shown as a reference example.

Note that the molecule that is not electrically neutral is frequentlycalled a molecular ion; however, unlike a gaseous state, it is difficultto quantitate the valence of molecule because the molecular discussedhere is one introduced inside a crystal lattice. Thus, a molecule thatis not electrically neutral is called molecular for convenience.

FIG. 14 shows that when an NO₂ molecule is introduced, the NO₂ moleculetends to be in a linear arrangement in the case where the charge of themodel is +1. FIG. 14 also shows that the angle of the O—N—O bond of themodel whose charge is −1 is smaller than that of the model whose chargeis neutral, and the angle of the O—N—O bond of the model whose charge isneutral is smaller than that of the model whose charge is +1. Thisstructure change in the NO₂ molecule is almost equal to a change in thebonding angle when the charge number of isolated molecules in a gasphase varies. Thus, it is suggested that almost the assumed charges areattributed to the NO₂ molecule, and the NO₂ molecule in SiO₂ probablyexists in a state close to an isolated molecule.

Next, as for the model in which an N₂O molecule was introduced into aninterstitial site in the c-SiO₂ model, a structure after the structureoptimization calculation was performed and structural parameters of theN₂O molecule are shown in FIG. 15. In FIG. 15, structural parameters ofthe N₂O molecule in a gaseous state are also shown as a referenceexample.

According to FIG. 15, in the case where the charge of the model is +1and the case where the charge is neutral, the structures of the N₂Omolecules are both in a linear arrangement, which means the N₂Omolecules of two cases have almost the same structure. In contrast, inthe case where the charge of the model is −1, the N₂O molecule has abent shape, and the distance between N and O is longer than that of theabove two cases. This conceivable reason is that an electron enters theLUMO level that is π* orbital of the N₂O molecule.

Next, as for the model in which an NO molecule was introduced into aninterstitial site in the c-SiO₂ model, a structure after the structureoptimization calculation was performed and structural parameters of theNO molecule are shown in FIG. 16.

According to FIG. 16, the distance between N and O is short in the casewhere the charge of the model is +1, and the distance between a nitrogenatom and an oxygen atom is long in the case where the charge of themodel is −1. This tendency is probably caused by the following reason.In the case where the charge of the NO molecule in a gaseous state is+1, the bond order of the N—O bond is 3.0; in the case where the chargeof the NO molecule in a gaseous state is 0, the bond order is 2.5; andin the case where the charge of the NO molecule in a gaseous state is−1, the bond order is 2.0. Thus, the bond order becomes the largest whenthe charge is +1. Therefore, the NO molecule in SiO₂ is considered toexist stably in a state close to the isolated molecule.

Then, as for the model in which an N atom was introduced into aninterstitial site in the c-SiO₂ model, a structure after the structureoptimization calculation was performed is shown in FIG. 17.

According to FIG. 17, in either charge state, the N atom that is bondedto atoms in SiO₂ is more stable in terms of energy than the N atomexists as an isolated atom in an interstitial site.

Next, the calculation of a transition level was performed on eachsample.

The transition level ε(q/q′) for transition between the charge q stateand the charge q′ state in a model having defect D in its structure canbe calculated with Formula 3.

$\begin{matrix}{\mspace{20mu}{{{ɛ\left( {q/q^{\prime}} \right)} = \frac{{\Delta\; E^{q}} - {\Delta\; E^{q^{\prime}}}}{q^{\prime} - q}}{{\Delta\; E^{q}} = {{E_{tot}\left( D^{q} \right)} - {E_{tot}({bulk})} + {\sum\limits_{i}\;{n_{i}\mu_{i}}} + {q\left( {ɛ_{VBM} + {\Delta\; V_{q}} + E_{f}} \right)}}}}} & \left\lbrack {{Formula}\mspace{14mu} 3} \right\rbrack\end{matrix}$

In the above formula, E_(tot) (D^(q)) represents the total energy in themodel having defect D of the charge q, E_(tot) (bulk) represents thetotal energy in a model without defects, n_(i) represents the number ofatoms i contributing to defects, μ_(i) represents the chemical potentialof atom i, ε_(VBM) represents the energy of the valence band maximum inthe model without defects, ΔV_(q) represents the correction termrelating to the electrostatic potential, and E_(f) represents the Fermienergy.

FIG. 18 is a band diagram showing the transition levels obtained fromthe above formula. As the oxide semiconductor film, an oxidesemiconductor film (hereinafter referred to as IGZO(111)) formed usingmetal oxide having an atomic ratio of In:Ga:Zn=1:1:1 is used. In FIG.18, a band diagram of the IGZO(111) is shown in addition to the banddiagrams of the above four models. The unit of the values in FIG. 18 is“eV”.

In FIG. 18, the value of each transition level indicates a valueobtained when the valence band maximum of SiO₂ is considered as a base(0.0 eV). Although a reference value was used as an electron affinity ofSiO₂ here, the practical positional relation of the bands in the casewhere SiO₂ is bonded to the IGZO(111) is affected by the electronaffinity of SiO₂ in some cases.

Hereinafter, the transition level that transits between a state wherethe charge of the model is +1 and a state where the charge of the modelis 0 is referred to as (+/0), and the transition level that transitsbetween a state where the charge of the model is 0 and a state where thecharge of system is −1 is referred to as (0/−).

According to FIG. 18, in the model in which an NO₂ molecule wasintroduced into SiO₂, two transition levels of (+/0) and (0/−) exist atthe positions within the band gap of the IGZO(111), which suggests thatthe NO₂ molecule may relate to trap and detrap of electrons. In both amodel in which an NO molecule was introduced into SiO₂ and a model inwhich an N atom was introduced into SiO₂, the transition level of (+/0)exists at a position within the band gap of the IGZO(111). In contrast,the transition level of the model in which an N₂O molecule wasintroduced into SiO₂ exists outside of the band gap of the IGZO(111),and the N₂O molecules probably exist stably as neutral moleculesregardless of the position on the Fermi level.

The above results strongly suggest that interstitial moleculescontaining nitrogen, which relate to trap and detrap of electrons causedby a shift of the threshold voltage of a transistor in the positivedirection, have the transition level at a position on the conductionband side within the band gap of the IGZO(111). Here, a molecule havinga transition level at a position close to the conduction band in theband gap of the IGZO(111) is probably an NO₂ molecule or an NO molecule,or both.

<1-2. Examination of ESR Signal>

Following the calculation results of the transition level, ESR signalsof NO₂ molecules were calculated. In addition, a model in which an Natom substituted for an oxygen atom in SiO₂ was examined in a mannersimilar to that of the above case.

In this case, an N atom has seven electrons, and an O atom has eightelectrons; in other words, an electron structure of the NO₂ molecule hasan open shell. Thus, the neutral NO₂ molecule has a lone electron, andcan be measured by ESR. In the case where an N atom substitutes for an Oatom in SiO₂, only two Si atoms exist around an N atom and the N atomincludes a dangling bond. Thus, the case can also be measured by ESR.Furthermore, ¹⁴N has only one nuclear spin, and a peak of ESR signalrelating to ¹⁴N is split into three. At this time, the split width ofESR signal is a hyperfine coupling constant.

Thus, calculation was performed to examine whether split of an ESRsignal of the oxide insulating film into three is caused by the NO₂molecule or the N atom that replaces an O atom in SiO₂. When an SiO₂crystal structure is used as a model, the amount of calculation isenormous. Thus, in this case, two kinds of models of cluster structuresas shown in FIGS. 19A and 19B were used, the structure optimization wasperformed on these models, and then, g-factors and hyperfine couplingconstants were calculated. FIG. 19A shows a model of an NO₂ molecule ina neutral state, and FIG. 19B shows a cluster model including an Si—N—Sibond. Note that the model shown in FIG. 19B is a cluster model in whicha dangling bond of an Si atom is terminated with an H atom.

Amsterdam density functional (ADF) software was used for structureoptimization of the models and calculation of the g-factors andhyperfine coupling constants of the models whose structures wereoptimized. In the structure optimization and the calculation of themodels and the g-factors and hyperfine coupling constants of the modelswhose structures were optimized, “GGA:BP” was used as a functional, and“QZ4P” was used as a basic function, and “None” was used as Core Type.In addition, in the calculation of the g-factors and hyperfine couplingconstants, “Spin-Orbit” was considered as a relativistic effect, and asa calculation method of ESR/EPR, “g & A-Tensor (full SO)” was employed.The calculation conditions are as follows.

TABLE 2 Software ADF Basis function QZ4P Functional GGA-BP Core TypeNone Relativistic Effect Spin-Orbit Calculation method g & A-Tensor ofESR/EPR (full SO)

As a result of structure optimization, in the case of the NO₂ moleculeshown in FIG. 19A, the bonding distance of the N—O bond was 0.1205 nm,and the angle of the O—N—O bond was 134.1°, which are close toexperimental values of the NO₂ molecule (the bonding distance: 0.1197nm, and the bonding angle 134.3°). In the case of the Si—N—Si clustermodel shown in FIG. 19B, the bonding distance of Si—N was 0.172 nm andthe angle of the Si—N—Si bond was 138.3°, which were almost the same asthe bonding distance of Si—N (0.170 nm) and the angle of the Si—N—Sibond (139.0°) in the structure that had been subjected to structureoptimization by first principles calculation in a state where an N atomsubstitutes for an O atom in the SiO₂ crystal.

The calculated g-factors and hyperfine coupling constants are shownbelow

TABLE 3 g-factor Hyperfine coupling constant [mT] g_x g_y g_z g(average) A_x A_y A_z A (average) NO₂ 2.0066 1.9884 2.0014 1.9988 4.544.49 6.53 5.19 Si—N—Si 2.0021 2.0174 2.0056 2.0084 3.14 −0.61 −0.62 0.64

As described above, the hyperfine coupling constant A corresponds to thesplit width of a peak of the ESR signal. According to Table 3, theaverage value of the hyperfine coupling constant A of the NO₂ moleculeis approximately 5 mT. In the case of the Si—N—Si cluster model, onlyA_x in the hyperfine coupling constants A is a positive value, which isapproximately 3 mT. FIG. 20A and FIG. 20B show the ESR spectra of NO₂and Si—N—Si, respectively, which are calculated from the g-factor andthe hyperfine coupling constant A.

According to this result, the ESR spectrum that has three signals, ahyperfine structure constant of approximately 5 mT, and a g-factor ofapproximately 2, which are obtained by ESR measurement using an X-band,is obtained probably because of an NO₂ molecule in an SiO₇ crystal.Among three signals, the g-factor of the medium signal is approximately2.

<1-3. Consideration of Deterioration Mechanism of Transistor>

A mechanism of a phenomenon in which the threshold voltage of atransistor is shifted in the positive direction when a positive gate BTstress test (+GBT) is performed is considered below based on the aboveresults.

The mechanism is considered with reference to FIG. 21. FIG. 21illustrates a structure in which a gate (GE), a gate insulating film(GI), an oxide semiconductor film (OS), and a silicon oxynitride film(SiON) are stacked in this order. Here, a case where the siliconoxynitride film SiON that is positioned on the back channel side of theoxide semiconductor film (OS) contains nitrogen oxide is described.

First, when the positive gate BT stress test (+GBT) is performed on thetransistor, the electron densities of the gate insulating film GI sideand the silicon oxynitride film SiON side of the oxide semiconductorfilm OS become higher. In the oxide semiconductor film OS, the siliconoxynitride film SiON side has a lower electron density than the gateinsulating film GI side. When an NO₂ molecule or an NO moleculecontained in the silicon oxynitride film SiON is diffused into theinterface between the gate insulating film GI and the oxidesemiconductor film OS and the interface between the oxide semiconductorfilm OS and the silicon oxynitride film SiON, electrons on the gateinsulating film GI side and the back channel side that are induced bythe positive gate BT stress test (+GBT) are trapped. As a result, thetrapped electrons remain in the vicinity of the interface between thegate insulating film GI and the oxide semiconductor film OS and theinterface between the oxide semiconductor film OS and the siliconoxynitride film SiON; thus, the threshold voltage of the transistor isshifted in the positive direction.

That is, a lower concentration of nitrogen oxide contained in thesilicon oxynitride film in contact with the oxide semiconductor film cansuppress a change in the threshold voltage of the transistor. Here, asspecific examples of the silicon oxynitride film in contact with theoxide semiconductor film, the protective film in contact with the backchannel side, the gate insulating film, and the like can be given. Byproviding the silicon oxynitride film containing an extremely smallamount of nitrogen oxide in contact with the oxide semiconductor film,the transistor can have excellent reliability.

<2. V_(O)H>

Next, an H atom (hereinafter referred to as V_(O)H) positioned in anoxygen vacancy V_(O), which is one of defects contained in the oxidesemiconductor film, is described.

<2-1. Energy and Stability Between Existing Modes of H>

First, the energy difference and stability in a mode of H that exists inan oxide semiconductor film is described with calculated results. Here,InGaZnO₄ (hereinafter referred to as IGZO(111)) was used as the oxidesemiconductor film.

The structure used for the calculation is based on an 84-atom bulk modelin which twice the number of a hexagonal unit cell of the IGZO(111) isarranged along the a-axis and b-axis.

As the bulk model, a model in which one O atom bonded to three In atomsand one Zn atom is replaced with an H atom was prepared (see FIG. 22A).FIG. 22B shows a diagram in which the a-b plane of the InO layer in FIG.22A is viewed from the c-axis direction. A region from which one O atombonded to three In atoms and one Zn atom is removed is shown as anoxygen vacancy V_(O), which is shown in a dashed line in FIGS. 22A and22B. In addition, an H atom in the oxygen vacancy V_(O) is expressed asV_(O)H.

In the bulk model, one O atom bonded to three In atoms and one Zn atomis removed, whereby an oxygen vacancy (V_(O)) is formed. A model inwhich, in the vicinity of the oxygen vacancy V_(O), an H atom is bondedto one O atom to which one Ga atom and two Zn atoms are bonded on thea-b plane was prepared (see FIG. 22C). FIG. 22D shows a diagram in whichthe a-b plane of the InO layer in FIG. 22C is viewed from the c-axisdirection. In FIGS. 22C and 22D, an oxygen vacancy V_(O) is shown in adashed line. A model in which an oxygen vacancy V_(O) is formed and, inthe vicinity of the oxygen vacancy V_(O), an H atom is bonded to one Oatom to which one Ga atom and two Zn atoms are bonded on the a-b planeis expressed as V_(O)+H.

Optimization calculation was performed on the above two models with afixed lattice constant to calculate the total energy. Note that as thevalue of the total energy is smaller, the structure becomes more stable.

In the calculation, first principles calculation software VASP (TheVienna Ab initio simulation Package) was used. The calculationconditions are shown in Table 4.

TABLE 4 Software VASP Pseudopotential PAW method Functional GGA/PBECut-off energy 500 eV k-point 4 × 4 × 1

As pseudopotential calculation of electronic states, a potentialgenerated by a projector augmented wave (PAW) method was used, and as afunctional, generalized-gradient-approximation/Perdew-Burke-Emzerhof(GGA/PBE) was used.

In addition, the total energy of the two models that were obtained bythe calculations is shown in Table 5.

TABLE 5 Model Total energy VoH −456.084 eV Vo + H −455.304 eV

According to Table 5, the total energy of V_(O)H is lower than that ofV_(O)+H by 0.78 eV. Thus, V_(O)H is more stable than V_(O)+H. Thissuggests that, when an H atom comes close to an oxygen vacancy (V_(O)),the H atom is easily trapped in the oxygen vacancy (V_(O)) than bondingwith an O atom.

<2-2. Thermodynamic State of V_(O)H>

Next, the thermodynamic state of V_(O)H, which is an H atom trapped inan oxygen vacancy (V_(O)), is evaluated with electronic statecalculation, and the results are described.

The formation energies of the defects V_(O)H contained in the IGZO(111),(V_(O)H)⁺, (V_(O)H)⁻, and (V_(O)H)⁰, were calculated. Note that(V_(O)H)⁺ represents a state in which a defect releases one electron,(V_(O)H)⁻ represents a state in which a defect traps one electron, and(V_(O)H)⁰ represents a state in which no electron is transferred.

In the calculation, the first principles calculation software VASP wasused. The calculation conditions are shown in Table 6. FIG. 23illustrates a model that was used for the calculation. The formationenergy was calculated on the assumption of the reaction in Formula 4. Aspseudopotential calculation of electronic states, a potential generatedby a PAW method was used, and as a functional, Heyd-Scuseria-Emzerhof(HSE) DFT hybrid factor (HSE06) was used. Note that the formation energyof an oxygen vacancy was calculated as follows: a dilute limit of theconcentration of oxygen vacancies was assumed, and excessive expansionof electrons and holes to the conduction band and the valence band wascorrected. In addition, shift of the valence band due to the defectstructure was corrected using the average electrostatic potential withthe valence band maximum of a complete crystal serving as the origin ofenergy.

TABLE 6 Software VASP Pseudopotential PAW method Functional HSE06Cut-off energy 800 eV The number 2 × 2 × 1 of k-point (optimization)samples 4 × 4 × 1 (single) Spin Polarized Shielding parameter 0.2Exchange term 0.25 mixing ratio The number of atoms 84

$\begin{matrix}{\left. {IGZO}\rightarrow{{IGZO}:{{VoH} + {\frac{1}{2}O_{2}} - {\frac{1}{2}H_{2}}}} \right.{{E_{form}\left( {{IGZO}:{VoH}} \right)} = {{E_{tot}\left( {{IGZO}:{VoH}} \right)} - {E_{tot}({IGZO})} + {\frac{1}{2}{E_{tot}\left( O_{2} \right)}} - {\frac{1}{2}{E_{tot}\left( H_{2} \right)}}}}} & \left\lbrack {{Formula}\mspace{14mu} 4} \right\rbrack\end{matrix}$

The formation energy obtained by the calculation is shown in FIG. 24A.

FIG. 24A shows the formation energies of (V_(O)H)⁺, (V_(O)H)⁻, and(V_(O)H)⁰. The lateral axis represents the Fermi level, and thelongitudinal axis represents the formation energy. The dotted linerepresents the formation energy of (V_(O)H)⁺, the solid line representsthe formation energy of (V_(O)H)⁰, and the dashed line represents theformation energy of (V_(O)H)⁻. In addition, the transition level of theV_(O)H charge from (V_(O)H)⁺ to (V_(O)H)⁻ through (V_(O)H)⁰ isrepresented by ε(+/−).

FIG. 24B shows a thermodynamic transition level of V_(O)H. From thecalculation result, the energy gap of InGaZnO₄ was 2.739 eV. Inaddition, when the energy of the valence band is 0 eV, the transferlevel (ε(+/−)) is 2.62 eV, which exists just under the conduction band.These suggest that in the case where the Fermi level exists in theenergy gap, the charge state of V_(O)H is always +1 and V_(O)H serves asa donor. This shows that IGZO(111) becomes n-type by trapping an H atomin an oxygen vacancy (V_(O)).

Next, FIG. 25 shows the evaluation results of the relationship betweenthe carrier (electron) density and the defect (V_(O)H) density.

FIG. 25 shows that the carrier density increases as the defect (V_(O)H)density increases.

Accordingly, it is found that V_(O)H in the IGZO(111) serves as a donor.In addition, it is also found that when the density of V_(O)H becomeshigh, the IGZO(111) becomes n-type.

<3. Model Explaining Relationship between DOS in Oxide SemiconductorFilm and Element to Be DOS>

When density of states (DOS) exists inside an oxide semiconductor filmand in the vicinity of the interface between the oxide semiconductorfilm and the outside, DOS can cause deterioration of a transistorincluding the oxide semiconductor film. The DOS inside the oxidesemiconductor film and in the vicinity of the interface with the oxidesemiconductor film can be explained on the basis of the positions of andthe bonding relation among oxygen (O), an oxygen vacancy (V_(O)),hydrogen (H), and nitrogen oxide (NO_(x)). A concept of a model isdescribed below.

In order to fabricate a transistor with stable electricalcharacteristics, it is important to reduce the DOS inside the oxidesemiconductor film and in the vicinity of the interface (to make ahighly purified intrinsic state). In order to reduce the DOS, oxygenvacancies, hydrogen, and nitrogen oxide should be reduced. Arelationship between DOS, which exists inside the oxide semiconductorfilm and in the vicinity of the interface with the oxide semiconductorfilm, and an oxygen vacancy, hydrogen, and nitrogen oxide will bedescribed below with the use of a model.

FIG. 26 illustrates a band structure of DOS inside an oxidesemiconductor film and in the vicinity of the interface of the oxidesemiconductor film. The case where the oxide semiconductor film is theoxide semiconductor film (IGZO(111)) containing indium, gallium, andzinc is described below.

There are two types of DOS, DOS at a shallow level (shallow level DOS)and DOS at a deep level (deep level DOS). Note that in thisspecification, the shallow level DOS refers to DOS between energy at theconduction band minimum (Ec) and the mid gap. Thus, for example, theshallow level DOS is located closer to energy at the conduction bandminimum. Note that in this specification, the deep level DOS refers toDOS between energy at the valence band maximum (Ev) and the mid gap.Thus, for example, the deep level DOS is located closer to the mid gapthan to energy at the valence band maximum.

In the oxide semiconductor film, there are two types of shallow levelDOS. One is DOS in the vicinity of a surface of an oxide semiconductorfilm (at the interface with an insulating film (insulator) or in thevicinity of the interface with the insulating film), that is, surfaceshallow DOS. The other is DOS inside the oxide semiconductor film, thatis, bulk shallow DOS. Furthermore, as a type of the deep level DOS,there is DOS inside the oxide semiconductor film, that is, bulk deepDOS.

These types of DOS are likely to act as described below. The surfaceshallow DOS in the vicinity of the surface of an oxide semiconductorfilm is located at a shallow level from the conduction band minimum, andthus trap and loss of an electric charge are likely to occur easily inthe surface shallow DOS. The bulk shallow DOS inside the oxidesemiconductor film is located at a deep level from the conduction bandminimum as compared to the surface shallow DOS in the vicinity of thesurface of the oxide semiconductor film, and thus loss of an electriccharge does not easily occur in the bulk shallow DOS.

An element causing DOS in an oxide semiconductor film is describedbelow.

For example, when a silicon oxide film is formed over an oxidesemiconductor film, indium contained in the oxide semiconductor film istaken into the silicon oxide film and replaced with silicon to formshallow level DOS.

For example, in the interface between the oxide semiconductor film andthe silicon oxide film, a bond between oxygen and indium contained inthe oxide semiconductor film is broken and a bond between the oxygen andsilicon is generated. This is because the bonding energy between siliconand oxygen is higher than the bonding energy between indium and oxygen,and the valence of silicon (tetravalence) is larger than the valence ofindium (trivalence). Oxygen contained in the oxide semiconductor film istrapped by silicon, so that a site of oxygen that has been bonded toindium becomes an oxygen vacancy. In addition, this phenomenon occurssimilarly when silicon is contained inside the oxide semiconductor film,as well as in the surface. Such an oxygen vacancy forms deep level DOS.

Another cause as well as silicon can break the bond between indium andoxygen. For example, in an oxide semiconductor film containing indium,gallium, and zinc, the bond between indium and oxygen is weaker and cutmore easily than the bond between oxygen and gallium or zinc. For thisreason, the bond between indium and oxygen is broken by plasma damagesor damages due to sputtered particles, so that an oxygen vacancy can beproduced. The oxygen vacancy forms deep level DOS.

The deep level DOS can trap a hole and thus serve as a hole trap (holetrapping center). This means that the oxygen vacancy forms bulk deep DOSinside the oxide semiconductor film. Since such an oxygen vacancy formsbulk deep DOS, the oxygen vacancy is an instability factor to the oxidesemiconductor film.

Such deep level DOS due to an oxygen vacancy is one of causes forforming bulk shallow DOS in the oxide semiconductor film, which isdescribed below.

In addition, an oxygen vacancy in the oxide semiconductor film trapshydrogen to be metastable. That is, when an oxygen vacancy that is deeplevel DOS and is capable of trapping a hole traps hydrogen, the oxygenvacancy forms bulk shallow DOS and becomes metastable. As described in<Thermodynamic State of V_(O)H> of this embodiment, when an oxygenvacancy traps hydrogen, the oxygen vacancy is neutrally or positivelycharged. That is, V_(O)H, which is one bulk shallow DOS in the oxidesemiconductor film, releases an electron, to be neutrally or positivelycharged, which adversely affects the characteristics of a transistor.

It is important to reduce the density of oxygen vacancies to prevent anadverse effect on the characteristics of the transistor. Thus, bysupplying excess oxygen to the oxide semiconductor film, that is, byfilling oxygen vacancies with excess oxygen, the density of oxygenvacancies in the oxide semiconductor film can be lowered. In otherwords, the oxygen vacancies become stable by receiving excess oxygen.For example, when excess oxygen is included in the oxide semiconductorfilm or an insulating film provided near the interface with the oxidesemiconductor film, the excess oxygen can fill oxygen vacancies in theoxide semiconductor film, thereby effectively eliminating or reducingoxygen vacancies in the oxide semiconductor film.

As described above, the oxygen vacancy may become a metastable state ora stable state by hydrogen or oxygen.

As described in <Transition Level of NO_(x) in Oxide Insulating Film> ofthis embodiment, NO or NO₂, which is NO_(x), traps an electron includedin the oxide semiconductor film. Because NO or NO₂, which is NO_(x), issurface shallow DOS in the vicinity of the surface of the oxidesemiconductor film, when NO_(x) is included in the insulating film inthe vicinity of the interface with the oxide semiconductor film, thecharacteristics of a transistor are adversely affected.

It is important to reduce the content of NO_(x) in the insulating filmin the vicinity of the interface with the oxide semiconductor film toprevent an adverse effect on the characteristics of the transistor.

<3-1. Model of Hysteresis Deterioration in Dark State of TransistorIncluding Oxide Semiconductor Film>

A mechanism in deterioration of a transistor including an oxidesemiconductor film is described next. The transistor including an oxidesemiconductor film deteriorates differently depending on whether or notthe transistor is irradiated with light. When the transistor isirradiated with light, deterioration is likely to result from the bulkdeep DOS at the deep level inside the oxide semiconductor film. When thetransistor is not irradiated with light, deterioration is likely toresult from the surface shallow DOS at the shallow level in the vicinityof the surface of the oxide semiconductor film (at the interface with aninsulating film or in the vicinity thereof).

Thus, a state where the transistor including an oxide semiconductor filmis not irradiated with light (dark state) is described. In the darkstate, the deterioration mechanism of the transistor can be explained onthe basis of trapping and releasing of a charge by the surface shallowDOS at the shallow level in the vicinity of the surface of the oxidesemiconductor film (at the interface with an insulating film or in thevicinity of the interface). Note that here, a gate insulating film isdescribed as an insulating film provided in the vicinity of theinterface with the oxide semiconductor film.

FIG. 27 shows variation in a threshold voltage (V_(th)) when thetransistor including an oxide semiconductor film is subjected to a gatebias temperature (BT) stress test repeatedly in the dark state. Asapparent from FIG. 27, the threshold voltage is shifted to a positiveside by the positive gate BT (+GBT) stress test. Then, the transistor issubjected to a negative gate BT (−GBT) stress test, so that thethreshold voltage is shifted to a negative side and is substantiallyequal to the initial value (initial). In this manner, by repeating thepositive gate BT stress test and the negative gate BT stress testalternately, the threshold voltage is shifted positively and negatively(i.e., a hysteresis occurs). In other words, it is found that when thepositive gate BT stress test and the negative gate BT stress test arerepeated without light irradiation, the threshold voltage is shiftedalternately to a positive side and then a negative side, but the shiftfits in certain range as a whole.

The variation in the threshold voltage of the transistor due to the gateBT stress test in the dark state can be explained with the surfaceshallow DOS in the vicinity of the surface of an oxide semiconductorfilm. FIG. 28 illustrates a band structure of an oxide semiconductorfilm and flow charts corresponding to the band structure.

Before application of the gate BT stress (at the gate voltage (V_(g)) of0), the surface shallow DOS in the vicinity of the surface of an oxidesemiconductor film has energy higher than the Fermi level (E_(f)) and iselectrically neutral since an electron is not trapped (Step S101 in FIG.28), In Step S101, the threshold voltage measured at this time is set asan initial value before the gate BT stress is applied.

Next, the positive gate BT stress test (dark state) is performed. Whenthe positive gate voltage is applied, the conduction band is curved andthe energy of the surface shallow DOS in the vicinity of the surface ofthe oxide semiconductor film becomes lower than the Fermi level. Thus,an electron is trapped in the surface shallow DOS in the vicinity of thesurface of the oxide semiconductor film, so that the DOS is chargednegatively (Step S102 in FIG. 28).

Next, the application of stress is stopped such that the gate voltage is0. By the gate voltage at 0, the surface shallow DOS in the vicinity ofthe surface of an oxide semiconductor film has energy higher than theFermi level. However, it takes a long time for the electron trapped inthe surface shallow DOS in the vicinity of the surface of the oxidesemiconductor film to be released. Thus, the surface shallow DOS in thevicinity of the surface of the oxide semiconductor film remains chargednegatively (Step S103 in FIG. 28). At this time, a channel formationregion of the transistor is being subjected to application of a negativevoltage as well as the gate voltage. Accordingly, a gate voltage that ishigher than the initial value should be applied so as to turn on thetransistor, so that the threshold voltage is shifted to a positive side.In other words, the transistor tends to be normally off.

Next, a negative gate voltage is applied as the negative gate BT stresstest (dark state). When the negative gate voltage is applied, theconduction band is curved and the energy of the surface shallow DOS inthe vicinity of the surface of the oxide semiconductor film becomes muchhigher. Thus, the electron trapped in the surface shallow DOS in thevicinity of the surface of the oxide semiconductor film is released, sothat the DOS becomes electrically neutral (Step S104 in FIG. 28).

Next, the application of stress is stopped such that the gate voltage is0. The surface shallow DOS in the vicinity of the surface of an oxidesemiconductor film at this time has released the electron and iselectrically neutral (Step S101). Thus, the threshold voltage is shiftedto a positive side, so that it returns to the initial value before thegate BT stress tests. The negative gate BT test and the positive gate BTstress test are repeated in the dark state, so that the thresholdvoltage is shifted repeatedly to the positive side and to the negativeside. However, an electron trapped in the surface shallow DOS in thevicinity of the surface of an oxide semiconductor film at the time ofthe positive gate BT stress test is released at the time of the negativegate BT stress test; therefore, it is found that the threshold voltageis shifted within a certain range as a whole.

As described above, the shift in the threshold voltage of a transistordue to the gate BT stress test in the dark state can be explained on thebasis of the understanding of the surface shallow DOS in the vicinity ofthe surface of the oxide semiconductor film.

<3-2. Model of Deterioration in Bright State of Transistor IncludingOxide Semiconductor Film>

Then, a deterioration mechanism under light irradiation (bright state)is described here. The deterioration mechanism of the transistor in thebright state is explained on the basis of the trap and release of anelectron in the bulk deep DOS at the deep level in the oxidesemiconductor film.

FIG. 29 shows the shift in the threshold voltage (V_(th)) when the gateBT stress test is performed repeatedly on the transistor including anoxide semiconductor film in the bright state. As shown in FIG. 29, thethreshold voltage (V_(th)) is shifted from the initial value (initial)in the negative direction.

In FIG. 29, a value measured in the dark state without application ofthe gate BT stress is plotted as the initial value of the thresholdvoltage. Then, the threshold voltage is measured in the bright statewithout application of the gate BT stress. As a result, the thresholdvoltage in the bright state is shifted to a negative side greatly fromthe threshold voltage in the dark state. One of the conceivable factorsis that an electron and a hole are generated by light irradiation andthe generated electron is excited to the conduction band. In otherwords, even when the gate BT stress is not applied, the thresholdvoltage of the transistor including an oxide semiconductor film isshifted to a negative side by light irradiation, so that the transistoris easily normally on. In this case, as the energy gap of the oxidesemiconductor film is larger, or as fewer DOS exist in the gap, fewerelectrons are excited. For that reason, the shift in the thresholdvoltage due to light irradiation is small in that case.

Then, when the negative gate BT stress is applied under lightirradiation (−GBT), the threshold voltage is further shifted to anegative side.

After that, the positive gate BT (+GBT) stress test is performed underlight irradiation, so that the threshold voltage is shifted to apositive side.

Further, when the negative gate BT stress test and the positive gate BTstress test are repeated under light irradiation, the threshold voltageis shifted to a positive side and a negative side repeatedly; as aresult, it is found that the threshold voltage is shifted gradually to anegative side as a whole.

In the gate BT stress tests (where the positive gate BT stress test andthe negative gate BT stress test are repeated) in the bright state, amechanism of the shift in the threshold voltage of the transistor isexplained with reference to the band structures in FIG. 30 and FIG. 31.With reference to FIG. 30 and FIG. 31, the bulk deep DOS in the oxidesemiconductor film and the non-bridging oxygen hole centers (NBOHC1 andNBOHC2) in the gate insulating film are described. Note that thenon-bridging oxygen hole center (NBOHC1) is NBOHC that is located closerto the interface with the oxide semiconductor film (on the surface side)than the non-bridging oxygen hole center (NBOHC2) is.

Before the gate BT stress test and light irradiation (when the gatevoltage (V_(g)) is 0), the bulk deep DOS in the oxide semiconductor filmhas energy lower than the Fermi level (E_(f)), and is electricallyneutral since holes are not trapped (Step S111 in FIG. 30). At thistime, the threshold voltage measured in the dark state is regarded asthe initial value in the dark state.

Next, the oxide semiconductor film is irradiated with light withoutbeing subjected to the gate BT stress, so that electrons and holes aregenerated (Step S112 in FIG. 30). The generated electrons are excited tothe conduction band, so that the threshold voltage is shifted to anegative side (electrons are not described in the subsequent steps). Inaddition, the generated holes lower the quasi-Fermi level (E_(fp)) ofholes. Because the quasi-Fermi level (E_(fp)) of holes is lowered, holesare trapped in the bulk deep DOS inside the oxide semiconductor film(Step S113 in FIG. 30). Accordingly, under light irradiation without thegate BT stress test, the threshold voltage is shifted to the negativeside, so that the transistor easily becomes normally on, unlike thetransistor in the dark state.

Next, the negative gate BT stress test is performed under lightirradiation, so that an electric field gradient is generated and holestrapped in the bulk deep DOS inside the oxide semiconductor film areinjected to the non-bridging oxygen hole center (NBOHC1) in the gateinsulating film (Step S114 in FIG. 30). In addition, some holes moveinto the non-bridging oxygen hole centers (NBOHC2) further inside thegate insulating film by the electric field (Step S115 in FIG. 31). Themovement of holes from the non-bridging oxygen hole centers (NBOHC1) tothe non-bridging oxygen hole centers (NBOHC2) in the gate insulatingfilm progresses with time of the electric field application. The holesin the non-bridging oxygen hole centers (NBOHC1) and NBOHC2) in the gateinsulating film act as positively-charged fixed charges, and shift thethreshold voltage to the negative side, so that the transistor easilybecomes normally on.

Light irradiation and the negative gate BT stress test are described asdifferent steps for easy understanding, but the present invention is notconstrued as being limited to description in this embodiment. Forexample, Step S112 to Step S115 can occur in parallel.

Next, the positive gate BT stress test is performed under lightirradiation, and holes trapped in the bulk deep DOS inside the oxidesemiconductor film and holes in the non-bridging oxygen hole centers(NBOHC1) in the gate insulating film are released by the application ofthe positive gate voltage (Step S116 in FIG. 31). Thus, the thresholdvoltage is shifted to the positive side. Note that because thenon-bridging oxygen hole center (NBOHC2) in the gate insulating film isat the deep level in the gate insulating film, almost no holes in thenon-bridging oxygen hole centers (NBOHC2) are directly released evenwhen the positive gate BT stress test is in the bright state. In orderthat the holes in the non-bridging oxygen hole center (NBOHC2) in thegate insulating film can be released, the holes should move to thenon-bridging oxygen hole centers (NBOHC1) on the surface side. Themovement of a hole from the non-bridging oxygen hole center (NBOHC2) tothe non-bridging oxygen hole center (NBOHC1) in the gate insulating filmprogresses little by little with the time of electric field application.Therefore, the shift amount to the positive side of the thresholdvoltage is small, and the threshold voltage does not return completelyto the initial value.

In addition, the movement of a hole occurs between the non-bridgingoxygen hole center (NBOHC1) in the gate insulating film and the bulkdeep DOS inside the oxide semiconductor film. However, because manyholes have been trapped in the bulk deep DOS inside the oxidesemiconductor film, the whole electric charge amount of the oxidesemiconductor film and the gate insulating film can be hardly reduced.

Next, the negative gate BT stress test is performed again under lightirradiation, so that an electric field gradient occurs and holes trappedin the bulk deep DOS inside the oxide semiconductor film are injectedinto the non-bridging oxygen hole center (NBOHC1) in the gate insulatingfilm. In addition, some of the holes are injected into the non-bridgingoxygen hole center (NBOHC2) that is deeper inside the gate insulatingfilm by an electric field (Step S117 in FIG. 31). Note that the holes inthe non-bridging oxygen hole centers (NBOHC2) in the gate insulatingfilm, which have been injected thereinto in Step S115, are left withoutbeing released. Thus, holes are further injected, so that the number ofholes serving as fixed charges is further increased. The thresholdvoltage is further shifted to the negative side, so that the transistorfurther easily becomes normally on.

Next, the positive gate BT stress test is performed under lightirradiation, so that holes trapped in the bulk deep DOS in the oxidesemiconductor film and holes in the non-bridging oxygen hole center(NBOHC1) in the gate insulating film are released by application of thepositive gate voltage (Step S118 in FIG. 31). As a result, the thresholdvoltage is shifted to the positive side. However, the holes in thenon-bridging oxygen hole center (NBOHC2) in the gate insulating film arehardly released. Accordingly, the shift amount to the positive side ofthe threshold voltage is small, and the threshold voltage does notreturn completely to the initial value.

It is presumed that by repeating the negative gate BT stress test andthe positive gate BT stress test in the bright state as described above,the threshold voltage is gradually shifted to the negative side as awhole while the threshold voltage is shifted to the positive side andthe negative side repeatedly.

The shift of the threshold voltage of the transistor in the gate BTstress test in the bright state can be explained on the basis of thebulk deep DOS inside the oxide semiconductor film and the non-bridgingoxygen hole centers (NBOHC1 and NBOHC2) in the gate insulating film.

<3-3. Process Model of Dehydration, Dehydrogenation, and Oxygen Additionof Oxide Semiconductor Film>

In order to fabricate a transistor with stable electricalcharacteristics, it is important to reduce the DOS inside the oxidesemiconductor film and in the vicinity of the interface of the oxidesemiconductor film (to make a highly purified intrinsic state). Aprocess model where the oxide semiconductor film is highly purified tobe intrinsic is described below. Dehydration and dehydrogenation of theoxide semiconductor film are described first and then oxygen additionwhere an oxygen vacancy (V_(O)) is filled with oxygen is described.

Before a process model where the oxide semiconductor film is highlypurified to be intrinsic is described, the position at which an oxygenvacancy is likely to be generated in the oxide semiconductor film isdescribed. In the oxide semiconductor film containing indium, gallium,and zinc, the bond between indium and oxygen is broken most easily ascompared to the bond between gallium and oxygen and the bond betweenzinc and oxygen. Thus, a model where the bond between indium and oxygenis broken to form an oxygen vacancy is described below.

When the bond between indium and oxygen is broken, oxygen is releasedand a site of the oxygen that has been bonded to indium serves as anoxygen vacancy. The oxygen vacancy forms the deep level DOS at the deeplevel of the oxide semiconductor film. Because the oxygen vacancy in theoxide semiconductor film is instable, it traps oxygen or hydrogen to bestable. For this reason, when hydrogen exists near an oxygen vacancy,the oxygen vacancy traps hydrogen to become V_(O)H. The V_(O)H forms theshallow level DOS at the shallow level in the oxide semiconductor film.

Next, when oxygen comes close to the V_(O)H in the oxide semiconductorfilm, oxygen extracts hydrogen from V_(O)H to become a hydroxyl group(OH), so that hydrogen is released from the V_(O)H (see FIGS. 32A and32B). The oxygen can move in the oxide semiconductor film so as to comecloser to hydrogen by heat treatment and the like.

Further, when the hydroxyl group comes closer to another V_(O)H in theoxide semiconductor film, the hydroxyl group extracts hydrogen fromV_(O)H to become a water molecule (H₂O), so that hydrogen is releasedfrom V_(O)H (see FIGS. 32C and 32D). In this manner, one oxygen atomreleases two hydrogen atoms from the oxide semiconductor film. This isreferred to as dehydration or dehydrogenation of the oxide semiconductorfilm. By the dehydration or dehydrogenation, the shallow level DOS atthe shallow level in the oxide semiconductor film is reduced, and thedeep level DOS is formed.

Next, when oxygen comes close to an oxygen vacancy in the oxidesemiconductor film, oxygen is trapped by the oxygen vacancy, so that theoxygen vacancy disappears (see FIGS. 32E and 32F). This is referred toas oxygen addition in the oxide semiconductor film. By the oxygenaddition, the deep level DOS at the deep level in the oxidesemiconductor film is reduced.

As described above, when dehydration or dehydrogenation and oxygenaddition of the oxide semiconductor film are performed, the shallowlevel DOS and the deep level DOS in the oxide semiconductor film can bereduced. This process is referred to as a highly purification processfor making an intrinsic oxide semiconductor.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

(Embodiment 3)

In this embodiment, impurities included in an oxide semiconductor filmin a transistor and deterioration of the transistor characteristics aredescribed. In the description, the IGZO(111) is used for the oxidesemiconductor film and carbon is used as one of the impurities.

<1. Effect of Carbon in IGZO>

An electronic state was calculated on a model where a C atom wasintroduced into the IGZO(111).

For the calculation, an IGZO(111) crystal model (the number of atoms:112) shown in FIG. 33A was used.

Here, as the model where a C atom is included in the IGZO(111), as shownin FIG. 33A and Table 7, the following models were used: models in eachof which a C atom was put in the respective interstitial sites (1) to(6), a model where one In atom was replaced with a C atom, a model whereone Ga atom was replaced with a C atom, a model where one Zn atom wasreplaced with a C atom, and a model where one O atom was replaced with aC atom.

TABLE 7 Proximate Arrangement Position metal atoms (1) between (Ga, Zn)OGa4, Zn2 (2) and (Ga, Zn)O Ga2, Zn4 (3) between (Ga, Zn)O In3, Ga2, Zn1(4) and InO In3, Gal, Zn2 (5) In1, Ga2, Zn1 (6) In1, Ga1, Zn2<1-1. Model where C Atom was Put in Interstitial Site>

A stable configuration was examined by comparing the energy afterstructure optimization of the models where C atoms were put in therespective interstitial sites (1) to (6). The calculation conditions areshown in Table 8. Note that GGA was used for exchange-correlationfunction, and thus the band gap tended to be underestimated.

TABLE 8 Software VASP Model InGaZnO4 crystal (112 atoms) CalculationStructure optimization (fixed lattice constant) Functional GGA-PBEPseudopotential PAW method Cut-off energy 500 eV k-point 2 × 2 × 3(optimization), 3 × 3 × 4 (state density) 

The results of the structure optimization calculation of the modelswhere C atoms were put in the respective interstitial sites (1) to (6)are shown in Table 9.

TABLE 9 Energy Initial arrangement After optimization (relative value)(1) interstitial site (CO)o −618.511 eV (0.326 eV) (Ga4, Zn2) (M1 = Ga,M2 = Ga, M3 = Zn, M4 = Zn) (2) interstitial site interstitial site−615.091 eV (3.746 eV) (Ga2, Zn4) (Ga2, Zn4) (3) interstitial site (CO)o−618.640 eV (0.197 eV) (In3, Ga2, Zn1) (M1 = In, M2 = Ga, M3 = In, M4 =In) (4) interstitial site (CO)o −618.196 eV (0.641 eV) (In3, Ga1, Zn2)(M1 = In, M2 = Zn, M3 = In, M4 = In) (5) interstitial site bonded toIn1, O3 −618.140 eV (0.697 eV) (In1, Ga2, Zn1) (6) interstitial sitebonded to In1, O2 −618.837 eV (0.000 eV) (In1, Ga1, Zn2)

The interstitial sites were selected as the original position of a Catom. After the structure optimization was performed, a model where a Catom was put in the interstitial site (1), (3), or (4) had a (CO)_(O)defect structure as illustrated in FIG. 33C. Note that (CO)_(O) meansthat one O atom in the structure in FIG. 33B is replaced with CO, asillustrated in the structure in FIG. 33C. In the (CO)_(O) defectstructure, a C atom is bonded to an O atom. The C atom is bonded to anatom M₁ and an atom M₂. The O atom is bonded to an atom M₃ and an atomM₄. A model where a C atom was put in the interstitial site (5) or (6)has a structure in which a C atom was bonded to atoms in the IGZO(111).When the energy was compared, a C atom was more stable in the (CO)_(O)defect structure and in a structure where a C atom was bonded to theatoms in the IGZO(111) than in the interstitial site.

FIG. 34A shows a structure of the model that has the lowest energy andis the most stable (model where a C atom was put in the interstitialsite (6)) in the calculation. FIG. 34B shows the density of states. InFIG. 34B, when the Fermi level E_(f) is 0 eV in the lateral axis, thedensity of states of up-spin and down-spin are shown in the upper andlower sides of the Fermi level E_(f), respectively.

In the structure shown in FIG. 34A, a C atom is bonded to one In atomand two O atoms. In a model where an Si atom belonging to the same groupas a C atom was put in the interstitial site, the Si atom was bondedonly to an O atom. The results indicate that the difference in bondingstate between the Si atom and the C atom may be attributed todifferences of their ionic radiuses and electronegativity. In FIG. 34B,when the density of states from the conduction band minimum to the Fermilevel E_(f) is integrated, the density of states corresponds to twoelectrons. The Fermi level E_(f) is positioned on the side closer to thevacuum level than the conduction band minimum is by two electrons; thus,it is presumed that, when the C atom is put in the interstitial site,two electrons are released from the C atom, so that the IGZO(111)becomes n-type.

<1-2. Model where Metal Element was Replaced with C Atom>

FIGS. 35A and 35B show the optimal structure and density of states in amodel where one In atom was replaced with a C atom. Note that in thelateral axis of FIG. 35B, the Fermi level E_(f) is 0 eV.

In the structure of FIG. 35A, a C atom is bonded to three O atoms andpositioned in a plane of a triangle having O atoms as the vertexes.Although the sketch of the density of states illustrated in FIG. 35B isalmost the same as that of the density of states in the case of nodefect, the Fermi level E_(f) is positioned on the side closer to thevacuum level than the conduction band minimum is by one electron; thus,it is presumed that, when an In atom is replaced with a C atom, oneelectron is released from the C atom, so that the IGZO(111) becamen-type. This is probably because a trivalent In atom was replaced with atetravalent C atom.

FIGS. 36A and 36B show the optimal structure and density of states in amodel where one Ga atom was replaced with a C atom. Note that in thelateral axis of FIG. 36B, the Fermi level E_(f) is 0 eV.

In the structure of FIG. 36A, a C atom is bonded to four O atoms andpositioned in almost the center of a tetrahedron having O atoms as thevertexes. Although the sketch of the density of states illustrated inFIG. 36B is almost the same as that of the density of states in the caseof no defect, the Fermi level E_(f) is positioned on the side closer tothe vacuum level than the conduction band minimum is by one electron;thus, it is presumed that, when a Ga atom is replaced with a C atom, oneelectron is released from the C atom, so that the IGZO(111) becamen-type. This is probably because a trivalent Ga atom is replaced with atetravalent C atom.

FIGS. 37A and 37B show the optimal structure and density of states in amodel where one Zn atom was replaced with a C atom. Note that in thelateral axis of FIG. 37B, the Fermi level E_(f) is 0 eV.

In the structure of FIG. 37A, a C atom is bonded to three O atoms andpositioned in a plane of a triangle having O atoms as the vertexes.Although the sketch of the density of states illustrated in FIG. 37B isalmost the same as that of the density of states in the case of nodefect, the Fermi level E_(f) is positioned on the side closer to thevacuum level than the conduction band minimum is by two electrons; thus,it is presumed that, when a Zn atom is replaced with a C atom, twoelectrons are released from the C atom, so that the IGZO(111) becamen-type. This is probably because a divalent Zn atom was replaced with atetravalent C atom.

<1-3. Model where O Atom was Replaced with C Atom>

Next, whether an O atom can be replaced with a C atom was examined. Inthe case where one O atom is replaced with a C atom, there are four Oatom sites in consideration of a combination of metals that are bondingpartners of an O atom, and substitution models for the sites were formedand structure optimization calculation was performed. As a result, amodel where an O atom bonded to two Ga atoms and one Zn atom wasreplaced with a C atom was energetically stable.

The IGZO(111) formed in an oxygen atmosphere contains sufficient Oatoms. Models (1) and (2.) in Table 10 were examined to compare energiesneeded for a C atom to substitute for an O atom in the IGZO(111)containing much oxygen. The numbers of atoms of Model (1) and (2) wereequalized; after that, the total energy of each model was calculated.

TABLE 10 Model Existing mode (1)  [InGaZnO₄] + [CO₂] (2) [InGaZnO₄:Co] +3/2[O₂]

In order to find out the stable configuration of a C atom, the IGZO(111)containing much oxygen was assumed, and the total energy of models wherethe numbers of atoms are the same as each other were calculated.Calculation results are shown in Table 11.

TABLE 11 Total energy Model Existing mode (relative value) (No defect)[InGaZnO₄] + [CO₂] −637.446 eV (0.000 eV) C is put in [InGaZnO₄C] + [O₂]−628.695 eV (8.751 eV) interstitial site In is replaced[InGaZnO₄:C_(In)] + −632.759 eV (4.687 eV) with C 1/2[In₂O₃] + 1/4[O₂]Ga is replaced [InGaZnO₄:C_(Ga)] + −633.665 eV (3.781 eV) with C1/2[Ga₂O₃] + 1/4[O₂] Zn is replaced [InGaZnO₄:C_(Zn)] + −632.801 eV(4.645 eV) with C [ZnO] + 1/2[O₂] O is replaced [InGaZnO₄:C_(O)] +3/2[O₂] −626.620 eV (10.826 eV) with C

In Model (1) shown in Table 10, a C atom was contained in the IGZO(111)as CO₂. In Model (2) shown in Table 10, an O atom was replaced with a Catom in the IGZO(111).

The energy of Model (1) was calculated to be lower than that of Model(2) by approximately 10.8 eV, and thus Model (1) is more stable thanModel (2). This suggests that Model (1) is more likely to exist thanModel (2). That is, that presumably shows that an O atom is unlikely tobe replaced with a C atom and the state where an O atom is replaced witha C atom is unstable.

As shown in Table 11, it is presumed that, because the energy of a Gaatom is low; a C atom in the IGZO(111) is likely to substitute for a Gaatom and is unlikely to substitute for an O atom. Note that in Table 11,“IGZO:C_(atom)” means that the atom is replaced with a C atom inInGaZnO₄.

As a result, it is found that when a C atom is put in an interstitialsite or a C atom substitutes for a metal atom (In, Ga, or Zn), theIGZO(111) becomes n-type. Furthermore, it is presumed that theconfiguration becomes stable when a C atom in the IGZO(111) substitutesparticularly for a Ga atom.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

(Embodiment 4)

In this embodiment, a semiconductor device and a manufacturing methodthereof, which are different from those in Embodiment 1, are describedwith reference to drawings. A transistor 50 of this embodiment is atop-gate transistor, which is different from the transistor 10 inEmbodiment 1.

<1. Structure of Transistor>

FIGS. 38A to 38C are a top view and cross-sectional views of thetransistor 50. FIG. 38A is the top view of the transistor 50. FIG. 38Bis a cross-sectional view taken along dashed-dotted line A-B in FIG.38A. FIG. 38C is a cross-sectional view taken along dashed-dotted lineC-D in FIG. 38A. Note that in FIG. 38A, for simplicity, a substrate 51,a protective film 53, a gate insulating film 59, an insulating film 63,and the like are omitted.

The transistor 50 illustrated in FIGS. 38A to 38C includes an oxidesemiconductor film 55 over the protective film 53; a pair of electrodes57 and 58 in contact with the oxide semiconductor film 55; the gateinsulating film 59 in contact with the oxide semiconductor film 55 andthe pair of electrodes 57 and 58; and a gate electrode 61 overlappingwith the oxide semiconductor film 55 with the gate insulating film 59therebetween. The insulating film 63 may be provided over the protectivefilm 53, the pair of electrodes 57 and 58, the gate insulating film 59,and the gate electrode 61.

In this embodiment, a film in contact with the oxide semiconductor film55, typically, at least one of the protective film 53 and the gateinsulating film 59 is an oxide insulating film that contains nitrogenand has a small number of defects.

Typical examples of the oxide insulating film containing nitrogen andhaving a small number of defects include a silicon oxynitride film andan aluminum oxynitride film. Further, a “silicon oxynitride film” or an“aluminum oxynitride film” refers to a film that contains more oxygenthan nitrogen, and a “silicon nitride oxide film” or an “aluminumnitride oxide film” refers to a film that contains more nitrogen thanoxygen.

The oxide insulating film containing nitrogen and having a small numberof detects has a region or a portion where the amount of gas having amass-to-charge ratio m/z of 17 released by heat treatment is greaterthan the amount of nitrogen oxide (NO_(x), where x is greater than orequal to 0 and less than or equal to 2, preferably greater than or equalto 1 and less than or equal to 2) released by heat treatment. Typicalexamples of nitrogen oxide include nitrogen monoxide and nitrogendioxide. Alternatively, the oxide insulating film containing nitrogenand having a small number of defects has a region or a portion where theamount of gas having a mass-to-charge ratio m/z of 17 released by heattreatment is greater than the amount of gas having a mass-to-chargeratio m/z of 30 released by heat treatment. Alternatively, the oxideinsulating film containing nitrogen and having a small number of defectshas a region or a portion where the amount of gas having amass-to-charge ratio m/z of 17 released by heat treatment is greaterthan the amount of gas having a mass-to-charge ratio m/z of 46 releasedby heat treatment. Alternatively, the oxide insulating film containingnitrogen and having a small number of defects has a region or a portionwhere the amount of gas having a mass-to-charge ratio m/z of 17 releasedby heat treatment is greater than the sum of the amount of gas having amass-to-charge ratio m/z of 30 and the amount of gas having amass-to-charge ratio m/z of 46 released by heat treatment.

Further alternatively, the oxide insulating film containing nitrogen andhaving a small number of defects has a region or a portion where theamount of gas having a mass-to-charge ratio m/z of 30 released by heattreatment is less than or equal to the detection limit and where theamount of gas having a mass-to-charge ratio m/z of 17 released by heattreatment is greater than or equal to 1×10¹⁸ molecules/cm³ and less thanor equal to 5×10¹⁹ molecules/cm³. Alternatively, the oxide insulatingfilm containing nitrogen and having a small number of defects has aregion or a portion where the amount of gas having a mass-to-chargeratio m/z of 46 released by heat treatment is less than or equal to thedetection limit and where the amount of gas having a mass-to-chargeratio m/z of 17 released by heat treatment is greater than or equal to1×10¹⁸ molecules/cm³ and less than or equal to 5×10¹⁹ molecules/cm³.Alternatively, the oxide insulating film containing nitrogen and havinga small number of defects has a region or a portion where the amount ofgas having a mass-to-charge ratio m/z of 30 released by heat treatmentis less than or equal to the detection limit, where the amount of gashaving a mass-to-charge ratio m/z of 46 released by heat treatment isless than or equal to the detection limit, and where the amount of gashaving a mass-to-charge ratio m/z of 17 released by heat treatment isgreater than or equal to 1×10¹⁸ molecules/cm³ and less than or equal to5×10¹⁹ molecules/cm³.

A typical example of the gas having a mass-to-charge ratio m/z of 30includes nitrogen monoxide. A typical example of the gas having amass-to-charge ratio m/z of 17 includes ammonia. A typical example ofthe gas having a mass-to-charge ratio m/z of 46 includes nitrogendioxide.

In an ESR spectrum at 100 K or lower of the oxide insulating filmcontaining nitrogen and having a small number of defects, after heattreatment, a first signal that appears at a g-factor of greater than orequal to 2.037 and less than or equal to 2.039, a second signal thatappears at a g-factor of greater than or equal to 2.001 and less than orequal to 2.003, and a third signal that appears at a g-factor of greaterthan or equal to 1.964 and less than or equal to 1.966 are observed. Thesum of the spin densities of the first signal that appears at a g-factorof greater than or equal to 2.037 and less than or equal to 2.039, thesecond signal that appears at a g-factor of greater than or equal to2.001 and less than or equal to 2.003, and the third signal that appearsat a g-factor of greater than or equal to 1.964 and less than or equalto 1.966 is lower than 1×10¹⁸ spins/cm³, typically higher than or equalto 1×10¹⁷ spins/cm³ and lower than 1×10¹⁸ spins/cm³.

In the ESR spectrum at 100 K or lower, the first signal that appears ata g-factor of greater than or equal to 2.037 and less than or equal to2.039, the second signal that appears at a g-factor of greater than orequal to 2.001 and less than or equal to 2.003, and the third signalthat appears at a g-factor of greater than or equal to 1.964 and lessthan or equal to 1.966 correspond to signals attributed to nitrogenoxide (NO_(x); x is greater than or equal to 0 and less than or equal to2, preferably greater than or equal to 1 and less than or equal to 2).Typical examples of nitrogen oxide include nitrogen monoxide andnitrogen dioxide.

When at least one of the protective film 53 and the gate insulating film59 in contact with the oxide semiconductor film 55 contains a smallamount of nitrogen oxide as described above, the carrier trap at theinterface between the oxide semiconductor film 55 and the gateinsulating film 59 or the interface between the oxide semiconductor film55 and the protective film 53 can be inhibited. As a result, a change inthe threshold voltage of the transistor included in the semiconductordevice can be reduced, which leads to a reduced change in the electricalcharacteristics of the transistor.

At least one of the protective film 53 and the gate insulating film 59preferably has a nitrogen concentration measured by SIMS of lower thanor equal to 6×10²⁰ atoms/cm³. In that case, nitrogen oxide is unlikelyto be generated in at least one of the protective film 53 and the gateinsulating film 59, so that the carrier trap at the interface betweenthe oxide semiconductor film 55 and the gate insulating film 59 or theinterface between the oxide semiconductor film 55 and the protectivefilm 53 can be inhibited. Furthermore, a change in the threshold voltageof the transistor included in the semiconductor device can be reduced,which leads to a reduced change in the electrical characteristics of thetransistor.

The details of other components of the transistor 50 are describedbelow.

As the substrate 51, a substrate given as an example of the substrate 11of Embodiment 1 can be used as appropriate.

In the case where the gate insulating film 59 is formed of an oxideinsulating film containing nitrogen and having a small number ofdefects, the protective film 53 can be formed using an oxide insulatingfilm containing oxygen at a higher proportion than oxygen in thestoichiometric composition. The oxide insulating film containing oxygenat a higher proportion than oxygen in the stoichiometric composition candiffuse oxygen into an oxide semiconductor film by heat treatment. Astypical examples of the protective film 53, a silicon oxide film, asilicon oxynitride film, a silicon nitride oxide film, a gallium oxidefilm, a hafnium oxide film, an yttrium oxide film, an aluminum oxidefilm, an aluminum oxynitride film, and the like can be given.

The thickness of the protective film 53 is greater than or equal to 50nm, preferably greater than or equal to 200 nm and less than or equal to3000 nm, further preferably greater than or equal to 300 nm and lessthan or equal to 1000 nm. When the protective film 53 is formed thick,the number of oxygen molecules released from the protective film 53 canbe increased, and the interface state at the interface between the basethe protective film 53 and an oxide semiconductor film formed later canbe reduced.

Here, “to release part of oxygen by heating” means that the amount ofreleased oxygen by conversion into oxygen atoms is greater than or equalto 1×10¹⁸ atoms/cm³, preferably greater than or equal to 3×10²⁰atoms/cm³ in TDS analysis. Note that the temperature of the film surfacein the TDS analysis is preferably higher than or equal to 100° C. andlower than or equal to 700° C., or higher than or equal to 100° C. andlower than or equal to 500° C.

The oxide semiconductor film 55 can be formed in a manner similar tothat of the oxide semiconductor film 17 in Embodiment 1.

The pair of electrodes 57 and 58 can be formed in a manner similar tothat of the pair of electrodes 19 and 20 of Embodiment 1.

Note that although the pair of electrodes 57 and 58 are provided betweenthe oxide semiconductor film 55 and the gate insulating film 59 in thisembodiment, the pair of electrodes 57 and 58 may be provided between theprotective film 53 and the oxide semiconductor film 55.

In the case where the protective film 53 is formed using an oxideinsulating film containing nitrogen and having a small number ofdefects, the gate insulating film 59 can be formed to have asingle-layer structure or a stacked-layer structure using, for example,any of silicon oxide, silicon oxynitride, silicon nitride oxide, siliconnitride, aluminum oxide, hafnium oxide, gallium oxide, Ga-Zn-based metaloxide, and the like. Note that an oxide insulating film is preferablyused for at least a region of the gate insulating film 59, which is incontact with the oxide semiconductor film 55, in order to improvecharacteristics of the interface with the oxide semiconductor film 55.

Further, it is possible to prevent outward diffusion of oxygen from theoxide semiconductor film 55 and entry of hydrogen, water, or the likeinto the oxide semiconductor film 55 from the outside by providing aninsulating film having a blocking effect against oxygen, hydrogen,water, and the like as the gate insulating film 59. As for theinsulating film having a blocking effect against oxygen, hydrogen,water, and the like, an aluminum oxide film, an aluminum oxynitridefilm, a gallium oxide film, a gallium oxynitride film, an yttrium oxidefilm, an yttrium oxynitride film, a hafnium oxide film, and a hafniumoxynitride film can be given as examples.

The gate insulating film 59 may be formed using a high-k material suchas hafnium silicate (HfSiO_(x)), hafnium silicate to which nitrogen isadded (HfSi_(x)O_(y)N_(z)), hafnium aluminate to which nitrogen is added(HfAl_(x)O_(y)N_(z)), hafnium oxide, or yttrium oxide, so that gateleakage current of the transistor can be reduced.

The thickness of the gate insulating film 59 is, for example, greaterthan or equal to 5 nm and less than or equal to 400 nm, preferablygreater than or equal to 10 nm and less than or equal to 300 nm, furtherpreferably greater than or equal to 15 nm and less than or equal to 100nm.

The gate electrode 61 can be formed in a manner similar to that of thegate electrode 13 of Embodiment 1.

The insulating film 63 is formed with a single-layer structure or astacked structure using one or more of silicon oxide, siliconoxynitride, silicon nitride oxide, silicon nitride, aluminum oxide,aluminum oxynitride, aluminum nitride oxide, aluminum nitride, and thelike to a thickness greater than or equal to 30 nm and less than orequal to 500 nm, preferably greater than or equal to 100 nm and lessthan or equal to 400 nm.

Like the protective film 53, the insulating film 63 may have astacked-layer structure including an oxynitride insulating filmcontaining oxygen at a higher proportion than oxygen in thestoichiometric composition and an insulating film having a blockingeffect against oxygen, hydrogen, water, and the like. As the insulatingfilm having a blocking effect against oxygen, hydrogen, water, and thelike, an aluminum oxide film, an aluminum oxynitride film, a galliumoxide film, a gallium oxynitride film, an yttrium oxide film, an yttriumoxynitride film, a hafnium oxide film, a hafnium oxynitride film, and asilicon nitride film can be given as examples. In the case where suchinsulating films are used, in heat treatment, oxygen is supplied to theoxide semiconductor film 55 through the gate insulating film 59 and/orthe protective film 53, which enables a reduction in the interface statebetween the oxide semiconductor film 55 and the gate insulating film 59and/or the interface state between the oxide semiconductor film 55 andthe protective film 53. Furthermore, the number of oxygen vacancies inthe oxide semiconductor film 55 can be reduced.

<2. Method for Manufacturing Transistor>

Next, a method for manufacturing the transistor illustrated in FIGS. 38Ato 38C is described with reference to FIGS. 39A to 39D. In each of FIGS.39A to 39D, a cross-sectional view in the channel length direction alongdot-dashed line A-B in FIG. 38A and a cross-sectional view in thechannel width direction along dot-dashed line C-D in FIG. 38A are usedfor describing a method for manufacturing the transistor 50.

The protective film 53 is formed over the substrate 51 as illustrated inFIG. 39A. Then, the oxide semiconductor film 55 is formed over theprotective film 53.

The protective film 53 is formed by a sputtering method, a CVD method,or the like.

In the case where an oxide insulating film containing nitrogen andhaving a small number of defects is formed as the protective film 53, asilicon oxynitride film can be formed by a CVD method as an example ofthe oxide insulating film containing nitrogen and having a small numberof defects. In this case, a deposition gas containing silicon and anoxidizing gas are preferably used as a source gas. Typical examples ofthe deposition gas containing silicon include silane, disilane,trisilane, and silane fluoride. Examples of the oxidizing gas includedinitrogen monoxide and nitrogen dioxide.

In the case where an oxide insulating film from which part of oxygen isreleased by heating is formed as the protective film 53, the oxideinsulating film is preferably formed by a sputtering method using theconditions where the amount of oxygen in a deposition gas is large. Asthe deposition gas, oxygen, a mixed gas of oxygen and a rare gas, or thelike can be used. The concentration of oxygen in the deposition gas ispreferably higher than or equal to 6% and lower than or equal to 100% asa typical example.

Furthermore in the case where an oxide insulating film from which partof oxygen is released by heating is formed as the protective film 53, anoxide insulating film is formed by a CVD method as the oxide insulatingfilm from which part of oxygen is released by heating, and then oxygenis introduced into the oxide insulating film, so that the amount ofoxygen released by heating can be increased. Oxygen can be added to theoxide insulating film by ion implantation, ion doping, plasma treatment,or the like. In this embodiment, the oxide semiconductor film is notprovided below the protective film 53; accordingly, even when oxygen isintroduced into the protective film 53, the oxide semiconductor film isnot damaged. Thus, oxygen can be introduced into the protective film 53in contact with the oxide semiconductor film without damage to the oxidesemiconductor film.

In the case where an oxide insulating film is formed by a CVD method asthe protective film 53, hydrogen or water derived from a source gas issometimes mixed in the oxide insulating film. Thus, after the oxideinsulating film is formed by a plasma CVD method, heat treatment ispreferably performed for dehydrogenation or dehydration.

The oxide semiconductor film 55 can be formed as appropriate by aformation method similar to that of the oxide semiconductor film 17described in Embodiment 1.

In order to improve the orientation of the crystal parts in the CAAC-OSfilm, planarity of the surface of the protective film 53 serving as abase insulating film of the oxide semiconductor film is preferablyimproved. The protective film 53 can be made to have an average surfaceroughness (Ra) of 1 nm or less, 0.3 nm or less, or 0.1 nm or less as atypical example.

As planarization treatment for improving planarity of the surface of theprotective film 53, one or more can be selected from chemical mechanicalpolishing (CMP) treatment, dry etching treatment, plasma treatment (whatis called reverse sputtering), and the like. The plasma treatment is theone in which minute unevenness of the surface is reduced by introducingan inert gas such as an argon gas into a vacuum chamber and applying anelectric field so that a surface to be processed serves as a cathode.

Next, as illustrated in FIG. 39B, the pair of electrodes 57 and 58 areformed. The pair of electrodes 57 and 58 can be formed as appropriate bya formation method similar to those of the pair of electrodes 19 and 20described in Embodiment 1. Alternatively, the pair of electrodes 57 and58 can be formed by a printing method or an inkjet method.

Next, as illustrated in FIG. 39C, the gate insulating film 59 and thegate electrode 61 are formed. An insulating film is formed by asputtering method, a CVD method, an evaporation method, or the like, anda conductive film is formed over the insulating film by a sputteringmethod, a CVD method, an evaporation method, or the like. Then, a maskis formed over the conductive film by a photolithography process. Afterthat, parts of insulating film and the conductive film are etched usingthe mask to form the gate insulating film 59 and the gate electrode 61.After that, the mask is removed.

A film to be the gate insulating film 59 is formed by a sputteringmethod, a CVD method, an evaporation method, or the like. A film to bethe gate electrode 61 is formed by a sputtering method, a CVD method, anevaporation method, or the like.

In the case where an oxide insulating film containing nitrogen andhaving a small number of defects is formed as the film to be the gateinsulating film 59, the film can be formed using conditions similar tothose of the protective film 53 as appropriate.

Next, as illustrated in FIG. 39D, the insulating film 63 is formed overthe substrate 51, the pair of electrodes 57 and 58, the gate insulatingfilm 59, and the gate electrode 61. The base insulating film 63 can beformed as appropriate by a sputtering method, a CVD method, a printingmethod, a coating method, or the like.

Next, in a manner similar to that in Embodiment 1, heat treatment may beperformed. The heat treatment is performed typically at a temperaturehigher than or equal to 150° C. and lower than the strain point of thesubstrate, preferably higher than or equal to 250° C. and lower than orequal to 450° C., further preferably higher than or equal to 300° C. andlower than or equal to 450° C. [0436]

Through the above steps, a transistor in which a change in thresholdvoltage is reduced can be manufactured. Further, a transistor in which achange in electrical characteristics is reduced can be manufactured.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

<Modification Example 1>

Modification examples of the transistor 50 described in Embodiment 4 aredescribed with reference to FIGS. 40A and 40B. In each of thetransistors described in this modification example, a gate insulatingfilm or a protective film has a stacked-layer structure.

In a transistor 50 a illustrated in FIG. 40A, the protective film 53have a multi-layer structure. Specifically, in the protective film 53,an oxide insulating film 65 and an oxide insulating film 67 are stacked.The oxide insulating film 65 contains oxygen at a higher proportion thanoxygen in the stoichiometric composition. The oxide insulating film 67in contact with the oxide semiconductor film 55 contains nitrogen, has asmall number of defects, and can be used as at least one of theprotective film 53 and the gate insulating film 59 of the transistor 50.

The oxide insulating film 65 containing oxygen at a higher proportionthan oxygen in the stoichiometric composition has a thickness of greaterthan or equal to 50 nm, preferably greater than or equal to 200 nm andless than or equal to 3000 nm, further preferably greater than or equalto 300 nm and less than or equal to 1000 nm. When the oxide insulatingfilm 65 containing oxygen at a higher proportion than oxygen in thestoichiometric composition is formed thick, the number of releasedoxygen molecules in the oxide insulating film 65 containing oxygen at ahigher proportion than oxygen in the stoichiometric composition can beincreased, and the interface state at the interface between the oxideinsulating film 67 and the oxide semiconductor film 55 can be lowered.

For forming the oxide insulating film 65 containing oxygen at a higherproportion than oxygen in the stoichiometric composition, an oxideinsulating film from which part of oxygen is released by heating andwhich can be used as the protective film 53 can be used as appropriate.

Furthermore, the oxide insulating film 67 can be formed in the formationmanner of the oxide insulating film containing nitrogen and having asmall number of detects which can be used as the protective film 53 andthe gate insulating film 59 in the transistor 50.

The oxide insulating film 65 containing oxygen at a higher proportionthan oxygen in the stoichiometric composition and the oxide insulatingfilm 67 are formed, and the oxide semiconductor film 55 is formed overthe oxide insulating film 67. After that, heat treatment may beperformed. By the heat treatment, part of oxygen contained in the oxideinsulating film 65 containing oxygen at a higher proportion than oxygenin the stoichiometric composition can be diffused in the vicinity of theinterface between the oxide insulating film 67 and the oxidesemiconductor film 55. As a result, the interface state in the vicinityof the interface between the oxide insulating film 67 and the oxidesemiconductor film 55 can be lowered, so that a change in thresholdvoltage can be reduced.

The temperature of the heat treatment is typically higher than or equalto 150° C. and lower than the strain point of the substrate, preferablyhigher than or equal to 250° C. and lower than or equal to 450° C.,further preferably higher than or equal to 300° C. and lower than orequal to 450° C.

The heat treatment is performed under an inert gas atmosphere containingnitrogen or a rare gas such as helium, neon, argon, xenon, or krypton.Further, the heat treatment may be performed under an inert gasatmosphere first, and then under an oxygen atmosphere. It is preferablethat the above inert gas atmosphere and the above oxygen atmosphere donot contain hydrogen, water, and the like. The treatment time is 3minutes to 24 hours.

In a transistor 50 b illustrated in FIG. 40B, the gate insulating film59 has a stacked structure of an oxide insulating film 69 and a nitrideinsulating film 71 in this order, and the oxide insulating film 69 incontact with the oxide semiconductor film 55 is an oxide insulating filmcontaining nitrogen and having a small number of defects.

As the nitride insulating film 71, a film similar to the nitrideinsulating film 29 described in Modification Example 1 in Embodiment 1is preferably used. Thus, the physical thickness of the gate insulatingfilm 59 can be increased. This makes it possible to reduce a decrease inwithstand voltage of the transistor 50 b and furthermore increase thewithstand voltage, thereby reducing electrostatic discharge damage to asemiconductor device.

<Modification Example 2>

A modification example of the transistor 50 described in Embodiment 4 isdescribed with reference to FIGS. 41A to 41C. In this modificationexample, a transistor in which an oxide semiconductor film is providedbetween a gate insulating film and a pair of electrodes is described.

FIGS. 41A to 41C are a top view and cross-sectional views of atransistor 50 c included in a semiconductor device of one embodiment ofthe present invention. FIG. 41A is a top view, FIG. 41B is a schematiccross-sectional view taken along dot-dashed line A-B in FIG. 41A, andFIG. 41C is a schematic cross-sectional view taken along dot-dashed lineC-D in FIG. 41A.

The transistor 50 c illustrated in FIGS. 41B and 41C includes an oxidesemiconductor film 73 over the protective film 53; the oxidesemiconductor film 55 over the oxide semiconductor film 73; the pair ofelectrodes 57 and 58 in contact with the oxide semiconductor film 55 andthe oxide semiconductor film 73; an oxide semiconductor film 75 incontact with the oxide semiconductor film 55 and the pair of electrodes57 and 58; the gate insulating film 59 over the oxide semiconductor film75; and the gate electrode 61 overlapping with the oxide semiconductorfilm 55 with the gate insulating film 59 therebetween. The insulatingfilm 63 may be provided over the protective film 53, the pair ofelectrodes 57 and 58, the oxide semiconductor film 75, the gateinsulating film 59, and the gate electrode 61.

In the transistor 50 c, the protective film 53 has a projecting portion,and the stacked oxide semiconductor films 73 and 55 are provided overthe projecting portion of the protective film 53.

As illustrated in FIG. 41B, the oxide semiconductor film 75 is incontact with the top surface of the oxide semiconductor film 55 and thetop and side surfaces of the pair of electrodes 57 and 58. Asillustrated in FIG. 41C, the oxide semiconductor film 75 is in contactwith a side surface of the projecting portion of the protective film 53,a side surface of the oxide semiconductor film 73, and the top and sidesurfaces of the oxide semiconductor film 55.

As illustrated in FIG. 41C, in the channel width direction of thetransistor 50 c, the gate electrode 61 faces the top and side surfacesof the oxide semiconductor film 55 with the oxide semiconductor film 75and the gate insulating film 59 therebetween.

The gate electrode 61 electrically surrounds the oxide semiconductorfilm 55. With this structure, on-state current of the transistor 50 ccan be increased. Such a transistor structure is referred to as asurrounded channel (s-channel) structure. Note that in the s-channelstructure, current flows in the whole (bulk) of the oxide semiconductorfilm 55. Since current flows in an inner part of the oxide semiconductorfilm 55, the current is hardly affected by interface scattering, andhigh on-state current can be obtained. In addition, by making the oxidesemiconductor film 55 thick, on-state current can be increased.

In fabricating a transistor with a small channel length and a smallchannel width, when a pair of electrodes, an oxide semiconductor film,or the like is processed while a resist mask is reduced in size, thepair of electrodes, the oxide semiconductor film, or the like has around end portion (curved surface) in some cases. With this structure,the coverage with the oxide semiconductor film 75 and the gateinsulating film 59, which are to be formed over the oxide semiconductorfilm 55, can be improved. In addition, electric field concentrationwhich might occur at the edges of the pair of electrodes 57 and 58 canbe relaxed, which can suppress deterioration of the transistor.

In addition, by miniaturizing the transistor, higher integration andhigher density can be achieved. For example, the channel length of thetransistor is set to 100 nm or less, preferably 40 nm or less, furtherpreferably 30 nm or less, still further preferably 20 nm or less, andthe channel width of the transistor is set to 100 nm or less, preferably40 nm or less, further preferably 30 nm or less, still furtherpreferably 20 nm or less. The transistor of one embodiment of thepresent invention with the s-channel structure can increase on-statecurrent even in the case where the channel width thereof is shortened asdescribed above.

For the oxide semiconductor film 73, the material of the oxidesemiconductor film 46 described in Modification Example 4 in Embodiment1 can be used as appropriate. Before a film to be the oxidesemiconductor film 55 is formed in FIG. 39A, a film to be the oxidesemiconductor film 73 is formed. Then, a film to be the oxidesemiconductor film 73 and a film to be the oxide semiconductor film 55are processed, whereby the oxide semiconductor film 73 and the oxidesemiconductor film 55 can be obtained.

For the oxide semiconductor film 75, the material of the oxidesemiconductor film 47 described in Modification Example 4 in Embodiment1 can be used as appropriate. Before a film to be the gate insulatingfilm 59 is formed in FIG. 39C, a film to be the oxide semiconductor film75 is formed. Then, a film to be the gate insulating film 59 and a filmto be the gate electrode 61 are formed. After that, the films areprocessed at the same time, whereby the oxide semiconductor film 75, thegate insulating film 59, and the gate electrode 61 can be obtained.

The thickness of the oxide semiconductor film 73 may be set asappropriate as long as formation of an interface state at the interfacewith the oxide semiconductor film 55 is inhibited. For example, theoxide semiconductor film 55 includes a region whose thickness is largerthan that of the oxide semiconductor film 73, preferably 2 times ormore, further preferably 4 times or more, still further preferably 6times or more as large as that of the oxide semiconductor film 73. Notethat the above does not apply in the case where the on-state current ofthe transistor need not be increased, and the oxide semiconductor film73 may include a region whose thickness is equal to or greater than thatof the oxide semiconductor film 55.

The oxide semiconductor film 75 includes a region whose thickness is setas appropriate, in a manner similar to that of the oxide semiconductorfilm 73, as long as formation of an interface state at the interfacewith the oxide semiconductor film 55 is inhibited. For example, theoxide semiconductor film 75 includes a region whose thickness is smallerthan or equal to that of the oxide semiconductor film 73. If the oxidesemiconductor film 75 is thick, it may become difficult for the electricfield from the gate electrode 61 to reach the oxide semiconductor film55; thus, it is preferable that the oxide semiconductor film 75 be thin.For example, the oxide semiconductor film 75 includes a region thinnerthan the oxide semiconductor film 55. Note that the thickness of theoxide semiconductor film 75 is not limited to the above, and may be setas appropriate depending on a driving voltage of the transistor inconsideration of the withstand voltage of the gate insulating film 59.

High integration of a semiconductor device requires miniaturization of atransistor. However, it is known that miniaturization of a transistorcauses deterioration in electrical characteristics of the transistor. Adecrease in channel width causes a reduction in on-state current.

However, in the transistor of one embodiment of the present invention,as described above, the oxide semiconductor film 75 is formed to coverthe channel formation region of the oxide semiconductor film 55, and thechannel formation region and the gate insulating film 59 are not incontact with each other. Therefore, scattering of carries formed at theinterface between the oxide semiconductor film 55 and the gateinsulating film 59 can be suppressed, whereby on-state current of thetransistor can be increased.

In the case where an oxide semiconductor film is made intrinsic orsubstantially intrinsic, decrease in the number of carriers contained inthe oxide semiconductor film may reduce the field-effect mobility.However, in the transistor of one embodiment of the present invention, agate electric field is applied to the oxide semiconductor film 55 notonly in the vertical direction but also from the side surfaces. That is,the gate electric field is applied to the whole of the oxidesemiconductor film 55, whereby current flows in the bulk of the oxidesemiconductor films. It is thus possible to improve the field-effectmobility of the transistor while a change in electrical characteristicsis reduced by highly purified intrinsic properties.

In the transistor of one embodiment of the present invention, the oxidesemiconductor film 55 is formed over the oxide semiconductor film 73, sothat an interface state is less likely to be formed. In addition,impurities do not enter the oxide semiconductor film 55 from above andbelow because the oxide semiconductor film 55 are provided between theoxide semiconductor films 73 and 75. Thus, the oxide semiconductor film55 is surrounded by the oxide semiconductor film 73 and the oxidesemiconductor film 75 (also electrically surrounded by the gateelectrode 61), so that stabilization of the threshold voltage inaddition to the above-described improvement of on-state current of thetransistor is possible. As a result, current flowing between the sourceand the drain when the voltage of the gate electrode is 0 V can bereduced, which leads to lower power consumption. Further, the thresholdvoltage of the transistor becomes stable; thus, long-term reliability ofthe semiconductor device can be improved.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

(Embodiment 5)

In this embodiment, one embodiment that can be applied to the oxidesemiconductor film in any of the transistors included in thesemiconductor device described in the above embodiment is described.

The oxide semiconductor film may include one or more of the following:an oxide semiconductor having a single-crystal structure (hereinafterreferred to as a single-crystal oxide semiconductor); an oxidesemiconductor having a polycrystalline structure (hereinafter referredto as a polycrystalline oxide semiconductor); an oxide semiconductorhaving a microcrystalline structure (hereinafter referred to as amicrocrystalline oxide semiconductor), and an oxide semiconductor havingan amorphous structure (hereinafter referred to as an amorphous oxidesemiconductor) Further, the oxide semiconductor film may be formed usinga CAAC-OS film. Furthermore, the oxide semiconductor film may include anamorphous oxide semiconductor and an oxide semiconductor having acrystal grain. Described below are the CAAC-OS and the microcrystallineoxide semiconductor.

An oxide semiconductor is classified into, for example, anon-single-crystal oxide semiconductor and a single crystal oxidesemiconductor. Alternatively, an oxide semiconductor is classified into,for example, a crystalline oxide semiconductor and an amorphous oxidesemiconductor.

Examples of a non-single-crystal oxide semiconductor include a c-axisaligned crystalline oxide semiconductor (CAAC-OS), a polycrystallineoxide semiconductor, a microcrystalline oxide semiconductor, and anamorphous oxide semiconductor. In addition, examples of a crystallineoxide semiconductor include a single crystal oxide semiconductor, aCAAC-OS, a polycrystalline oxide semiconductor, and a microcrystallineoxide semiconductor.

Described below are the CAAC-OS, the microcrystalline oxidesemiconductor, and the amorphous oxide semiconductor.

First, a CAAC-OS is described.

A CAAC-OS is one of oxide semiconductors having a plurality of c-axisaligned crystal parts (also referred to as pellets).

In a transmission electron microscope (TEM) image of the CAAC-OS, aboundary between crystal parts, that is, a clear grain boundary is notobserved. Thus, in the CAAC-OS, a reduction in electron mobility due tothe grain boundary is less likely to occur.

FIG. 73A shows an example of a high-resolution TEM image of a crosssection of the CAAC-OS which is obtained from a direction substantiallyparallel to the sample surface. Here, the TEM image is obtained with aspherical aberration corrector function. The high-resolution TEM imageobtained with a spherical aberration corrector function is particularlyreferred to as a Cs-corrected high-resolution TEM image in the followingdescription. Note that the Cs-corrected high-resolution TEM image can beobtained with, for example, an atomic resolution analytical electronmicroscope JEM-ARM200F manufactured by JEOL Ltd.

FIG. 73B is an enlarged Cs-corrected high-resolution TEM image of aregion (1) in FIG. 73A. FIG. 73B shows that metal atoms are arranged ina layered manner in a crystal part. Each metal atom layer has aconfiguration reflecting unevenness of a surface over which the CAAC-OSis formed (hereinafter, the surface is referred to as a formationsurface) or a top surface of the CAAC-OS, and is arranged parallel tothe formation surface or the top surface of the CAAC-OS.

As shown in FIG. 73B, the CAAC-OS has a characteristic atomicarrangement. The characteristic atomic arrangement is denoted by anauxiliary line in FIG. 73C. FIGS. 73B and 73C prove that the size of apellet is approximately 1 nm to 3 nm, and the size of a space caused bytilt of the pellets is approximately 0.8 nm. Therefore, the pellet canalso be referred to as a nanocrystal (nc).

Here, according to the Cs-corrected high-resolution TEM images, theschematic arrangement of pellets 5100 of a CAAC-OS over a substrate 5120is illustrated by such a structure in which bricks or blocks are stacked(see FIG. 73D). The part in which the pellets are tilted as observed inFIG. 73C corresponds to a region 5161 shown in FIG. 73D.

For example, as shown in FIG. 74A, a Cs-corrected high-resolution TEMimage of a plane of the CAAC-OS obtained from a direction substantiallyperpendicular to the sample surface is observed. FIGS. 74B, 74C, and 74Dare enlarged Cs-corrected high-resolution TEM images of regions (1),(2), and (3) in FIG. 74A, respectively. FIGS. 74B, 74C, and 74D indicatethat metal atoms are arranged in a triangular, quadrangular, orhexagonal configuration in a crystal part. However, there is noregularity of arrangement of metal atoms between different crystalparts.

FIG. 70A is a high-resolution cross-sectional TEM image of a CAAC-OS.FIG. 70B is a high-resolution cross-sectional TEM image obtained byenlarging the image of FIG. 70A. In FIG. 70B, atomic arrangement ishighlighted for easy understanding.

FIG. 70C is local Fourier transform images of regions each surrounded bya circle (the diameter is about 4 nm) between A and O and between O andA′ in FIG. 70A. C-axis alignment can be observed in each region in FIG.70C. The c-axis direction between A and O is different from that betweenO and A′, which indicates that a grain in the region between A and O isdifferent from that between O and N. In addition, the angle of thec-axis between A and O continuously and gradually changes, for example,14.3°, 16.6°, and 26.4°. Similarly, the angle of the c-axis between Oand A′ continuously changes, for example, −18.3°, −17.6°, and −15.9°.

Note that in an electron diffraction pattern of the CAAC-OS, spots(luminescent spots) indicating alignment are observed. For example, whenelectron diffraction with an electron beam having a diameter of 1 nm ormore and 30 nm or less (such electron diffraction is also referred to asnanobeam electron diffraction) is performed on the top surface of theCAAC-OS, spots are observed (see FIG. 71A).

The results of the high-resolution cross-sectional TEM image and thehigh-resolution plan TEM image show that the crystal parts in theCAAC-OS have alignment.

Most of the crystal parts included in the CAAC-OS each fit inside a cubewhose one side is less than 100 nm. Thus, there is a case where acrystal part included in the CAAC-OS fits inside a cube whose one sideis less than 10 nm, less than 5 nm, or less than 3 nm. Note that when aplurality of crystal parts included in the CAAC-OS are connected to eachother, one large crystal region is formed in some cases. For example, acrystal region with an area of 2500 nm² or more, 5 μm² or more, or 1000μm² or more is observed in some cases in the high-resolution plan TEMimage.

For example, when the structure of a CAAC-OS including an InGaZnO₄crystal is analyzed by an out-of-plane method using an X-ray diffraction(XRD) apparatus, a peak appears at a diffraction angle (2θ) of around31° as shown in FIG. 75A. This peak is derived from the (009) plane ofthe InGaZnO₄ crystal, which indicates that crystals in the CAAC-OS havec-axis alignment, and that the c-axes are aligned in a directionsubstantially perpendicular to the formation surface or the top surfaceof the CAAC-OS.

Note that in structural analysis of the CAAC-OS including an InGaZnO₄crystal by an out-of-plane method, another peak may appear when 2θ isaround 36°, in addition to the peak at 2θ of around 31°. The peak at 2θof around 36° indicates that a crystal having no c-axis alignment isincluded in part of the CAAC-OS. It is preferable that in the CAAC-OS, apeak appear when 2θ is around 31° and that a peak not appear when 2θ isaround 36°.

On the other hand, in structural analysis of the CAAC-OS by an in-planemethod in which an X-ray is incident on a sample in a directionsubstantially perpendicular to the c-axis, a peak appears when 2θ isaround 56°. This peak is attributed to the (110) plane of the InGaZnO₄crystal. In the case of the CAAC-OS, when analysis (ϕ scan) is performedwith 2θ fixed at around 56° and with the sample rotated using a normalvector of the sample surface as an axis (ϕ axis), as shown in FIG. 75B,a peak is not clearly observed. In contrast, in the case of a singlecrystal oxide semiconductor of InGaZnO₄, when ϕ scan is performed with2θ fixed at around 56°, as shown in FIG. 75C, six peaks which arederived from crystal planes equivalent to the (110) plane are observed.Accordingly, the structural analysis using XRD shows that the directionsof a-axes and b-axes are different in the CAAC-OS.

Next, FIG. 76A shows a diffraction pattern (also referred to as aselected-area transmission electron diffraction pattern) obtained insuch a manner that an electron beam with a probe diameter of 300 nm isincident on an In—Ga—Zn oxide that is a CAAC-OS in a direction parallelto the sample surface. As shown in FIG. 76A, for example, spots derivedfrom the (009) plane of an InGaZnO₄ crystal are observed. Thus, theelectron diffraction also indicates that pellets included in the CAAC-OShave c-axis alignment and that the c-axes are aligned in a directionsubstantially perpendicular to the formation surface or the top surfaceof the CAAC-OS. Meanwhile, FIG. 76B shows a diffraction pattern obtainedin such a manner that an electron beam with a probe diameter of 300 nmis incident on the same sample in a direction perpendicular to thesample surface. As shown in FIG. 76B, a ring-like diffraction pattern isobserved. Thus, the electron diffraction also indicates that the a-axesand b-axes of the pellets included in the CAAC-OS do not have regularalignment. The first ring in FIG. 76B is considered to be derived fromthe (010) plane, the (100) plane, and the like of the InGaZnO₄ crystal.The second ring in FIG. 76B is considered to be derived from the (110)plane and the like.

Since the c-axes of the pellets (nanocrystals) are aligned in adirection substantially perpendicular to the formation surface or thetop surface in the above manner, the CAAC-OS can also be referred to asan oxide semiconductor including c-axis aligned nanocrystals (CANC).

According to the above results, in the CAAC-OS having c-axis alignment,while the directions of a-axes and b-axes are different between crystalparts, the c-axes are aligned in a direction parallel to a normal vectorof a formation surface or a normal vector of a top surface. Thus, eachmetal atom layer arranged in a layered manner observed in thehigh-resolution cross-sectional TEM image corresponds to a planeparallel to the a-b plane of the crystal.

Note that the crystal part is formed concurrently with deposition of theCAAC-OS or is formed through crystallization treatment such as heattreatment. As described above, the c-axis of the crystal is aligned in adirection parallel to a normal vector of a formation surface or a normalvector of a top surface of the CAAC-OS. Thus, for example, in the casewhere a shape of the CAAC-OS is changed by etching or the like, thec-axis might not be necessarily parallel to a normal vector of aformation surface or a normal vector of a top surface of the CAAC-OS.

Distribution of c-axis aligned crystal parts in the CAAC-OS is notnecessarily uniform. For example, in the case where crystal growthleading to the crystal parts of the CAAC-OS occurs from the vicinity ofthe top surface of the CAAC-OS, the proportion of the c-axis alignedcrystal parts in the vicinity of the top surface is higher than that inthe vicinity of the formation surface in some cases. Furthermore, whenan impurity is added to the CAAC-OS, a region to which the impurity isadded is altered, and the proportion of the c-axis aligned crystal partsin the CAAC-OS varies depending on regions, in some cases.

The CAAC-OS is an oxide semiconductor with a low impurity concentration.The impurity means an element other than the main components of theoxide semiconductor, such as hydrogen, carbon, silicon, or a transitionmetal element. An element (specifically, silicon or the like) havinghigher strength of bonding to oxygen than a metal element included in anoxide semiconductor extracts oxygen from the oxide semiconductor, whichresults in disorder of the atomic arrangement and reduced crystallinityof the oxide semiconductor. A heavy metal such as iron or nickel, argon,carbon dioxide, or the like has a large atomic radius (or molecularradius), and thus disturbs the atomic arrangement of the oxidesemiconductor and decreases crystallinity. Additionally, the impuritycontained in the oxide semiconductor might serve as a carrier trap or acarrier generation source.

Moreover, the CAAC-OS is an oxide semiconductor having a low density ofdefect states. For example, oxygen vacancies in the oxide semiconductorserve as carrier traps or serve as carrier generation sources whenhydrogen is captured therein.

In a transistor using the CAAC-OS, change in electrical characteristicsdue to irradiation with visible light or ultraviolet light is small.

A semiconductor device including the transistor having the CAAC-OS isless likely to be broken even when folded. For this reason, a flexiblesemiconductor device preferably includes the transistor having theCAAC-OS.

Next, a microcrystalline oxide semiconductor is described.

A microcrystalline oxide semiconductor has a region in which a crystalpart is observed and a region in which a crystal part is not clearlyobserved in a high-resolution TEM image. In most cases, the size of acrystal part included in the microcrystalline oxide semiconductor isgreater than or equal to 1 nm and less than or equal to 100 nm, orgreater than or equal to 1 nm and less than or equal to 10 nm. An oxidesemiconductor including a nanocrystal that is a microcrystal with a sizegreater than or equal to 1 nm and less than or equal to 10 nm, or a sizegreater than or equal to 1 nm and less than or equal to 3 nm isspecifically referred to as a nanocrystalline oxide semiconductor(nc-OS). In a high-resolution TEM image of the nc-OS, for example, agrain boundary is not clearly observed in some cases. Note that there isa possibility that the origin of the nanocrystal is the same as that ofa pellet in a CAAC-OS. Therefore, a crystal part of the nc-OS may bereferred to as a pellet in the following description.

In the nc-OS, a microscopic region (for example, a region with a sizegreater than or equal to 1 nm and less than or equal to 10 nm, inparticular, a region with a size greater than or equal to 1 nm and lessthan or equal to 3 nm) has a periodic atomic arrangement. There is noregularity of crystal orientation between different crystal parts in thenc-OS. Thus, the orientation of the whole film is not ordered.Accordingly, the nc-OS cannot be distinguished from an amorphous oxidesemiconductor, depending on an analysis method. For example, when thenc-OS is subjected to structural analysis by an out-of-plane method withan XRD apparatus using an X-ray having a diameter larger than the sizeof a crystal part, a peak which shows a crystal plane does not appear.Furthermore, a diffraction pattern like a halo pattern is observed whenthe nc-OS is subjected to electron diffraction using an electron beamwith a probe diameter (e.g., 50 nm or larger) that is larger than thesize of a crystal part (the electron diffraction is also referred to asselected-area electron diffraction). Meanwhile, spots appear in ananobeam electron diffraction pattern of the nc-OS when an electron beamhaving a probe diameter close to or smaller than the size of a crystalpart is applied. Moreover, in a nanobeam electron diffraction pattern ofthe nc-OS, regions with high luminance in a circular (ring) pattern areshown in some cases. Also in a nanobeam electron diffraction pattern ofthe nc-OS, a plurality of spots is shown in a ring-like region in somecases (see FIG. 71B).

Since there is no regularity of crystal orientation between the pellets(nanocrystals) as mentioned above, the nc-OS can also be referred to asan oxide semiconductor including non-aligned nanocrystals (NANC).

The nc-OS is an oxide semiconductor that has high regularity as comparedwith an amorphous oxide semiconductor. Therefore, the nc-OS is likely tohave a lower density of defect states than an amorphous oxidesemiconductor. Note that there is no regularity of crystal orientationbetween different crystal parts in the nc-OS. Therefore, the nc-OS has ahigher density of defect states than the CAAC-OS.

Note that an oxide semiconductor may be a stacked film including two ormore of an amorphous oxide semiconductor, a microcrystalline oxidesemiconductor, and a CAAC-OS, for example.

In the case where an oxide semiconductor film has a plurality ofstructures, the structures can be analyzed using nanobeam electrondiffraction in some cases.

FIG. 71C illustrates a transmission electron diffraction measurementapparatus which includes an electron gun chamber 310, an optical system312 below the electron gun chamber 310, a sample chamber 314 below theoptical system 312, an optical system 316 below the sample chamber 314,an observation chamber 320 below the optical system 316, a camera 318installed in the observation chamber 320, and a film chamber 322 belowthe observation chamber 320. The camera 318 is provided to face towardthe inside of the observation chamber 320. Note that the film chamber322 is not necessarily provided.

FIG. 71D illustrates an internal structure of the transmission electrondiffraction measurement apparatus illustrated in FIG. 71C. In thetransmission electron diffraction measurement apparatus, a substance 328which is positioned in the sample chamber 314 is irradiated withelectrons emitted from an electron gun installed in the electron gunchamber 310 through the optical system 312. Electrons passing throughthe substance 328 enter a fluorescent plate 332 provided in theobservation chamber 320 through the optical system 316. On thefluorescent plate 332, a pattern corresponding to the intensity of theincident electron appears, which allows measurement of a transmissionelectron diffraction pattern.

The camera 318 is installed so as to face the fluorescent plate 332 andcan take a picture of a pattern appearing in the fluorescent plate 332.An angle formed by a straight line which passes through the center of alens of the camera 318 and the center of the fluorescent plate 332 andan upper surface of the fluorescent plate 332 is, for example, 15° ormore and 80° or less, 30° or more and 75° or less, or 45° or more and70° or less. As the angle is reduced, distortion of the transmissionelectron diffraction pattern taken by the camera 318 becomes larger.Note that if the angle is obtained in advance, the distortion of anobtained transmission electron diffraction pattern can be corrected.Note that the film chamber 322 may be provided with the camera 318. Forexample, the camera 318 may be set in the film chamber 322 so as to beopposite to the incident direction of electrons 324. In this case, atransmission electron diffraction pattern with less distortion can betaken from the rear surface of the fluorescent plate 332.

A holder for fixing the substance 328 that is a sample is provided inthe sample chamber 314. The holder transmits electrons passing throughthe substance 328. The holder may have, for example, a function ofmoving the substance 328 in the direction of the X, Y, and Z axes. Themovement function of the holder may have an accuracy of moving thesubstance in the range of, for example, 1 nm to 10 nm, 5 nm to 50 nm, 10nm to 100 nm, 50 nm to 500 nm, and 100 nm to 1 μm. The range ispreferably determined to be an optimal range for the structure of thesubstance 328.

Then, a method for measuring a transmission electron diffraction patternof a substance by the transmission electron diffraction measurementapparatus described above will be described.

For example, changes in the structure of a substance can be observed bychanging (scanning) the irradiation position of the electrons 324 thatare a nanobeam in the substance, as illustrated in FIG. 71D. At thistime, when the substance 328 is a CAAC-OS film, a diffraction patternshown in FIG. 71A is observed. When the substance 328 is an nc-OS film,a diffraction pattern shown in FIG. 71B is observed.

Even when the substance 328 is a CAAC-OS film, a diffraction patternsimilar to that of an nc-OS film or the like is partly observed in somecases. Therefore, whether a CAAC-OS film is favorable can be determinedby the proportion of a region where a diffraction pattern of a CAAC-OSfilm is observed in a predetermined area (also referred to as proportionof CAAC). In the case of a high quality CAAC-OS for example, theproportion of CAAC is higher than or equal to 50%, preferably higherthan or equal to 80%, further preferably higher than or equal to 90%,still further preferably higher than or equal to 95%. Note that a regionwhere a diffraction pattern different from that of a CAAC-OS film isobserved is referred to as the proportion of non-CAAC.

For example, transmission electron diffraction patterns were obtained byscanning a top surface of a sample including a CAAC-OS film obtainedjust after deposition (represented as “as-sputtered”) and a top surfaceof a sample including a CAAC-OS film subjected to heat treatment at 450°C. in an atmosphere containing oxygen. Here, the proportion of CAAC wasobtained in such a manner that diffraction patterns were observed byscanning for 60 seconds at a rate of 5 nm/second and the obtaineddiffraction patterns were converted into still images every 0.5 seconds.Note that as an electron beam, a nanobeam with a probe diameter of 1 nmwas used. The above measurement was performed on six samples. Theproportion of CAAC was calculated using the average value of the sixsamples.

FIG. 72A shows the proportion of CAAC in each sample. The proportion ofCAAC of the CAAC-OS film obtained just after the deposition was 75.7%(the proportion of non-CAAC was 24.3%). The proportion of CAAC of theCAAC-OS film subjected to the heat treatment at 450° C. was 85.3% (theproportion of non-CAAC was 14.7%). These results show that theproportion of CAAC obtained after the heat treatment at 450° C. ishigher than that obtained just after the deposition. That is, heattreatment at high temperatures (e.g., higher than or equal to 400° C.)reduces the proportion of non-CAAC (increases the proportion of CAAC).Furthermore, the above results also indicate that even when thetemperature of the heat treatment is lower than 500° C., the CAAC-OSfilm can have a high proportion of CAAC.

Here, most of diffraction patterns different from that of a CAAC-OS filmare diffraction patterns similar to that of an nc-OS film. Furthermore,an amorphous oxide semiconductor film was not able to be observed in themeasurement region. Therefore, the above results suggest that the regionhaving a structure similar to that of an nc-OS film is rearranged by theheat treatment owing to the influence of the structure of the adjacentregion, whereby the region becomes CAAC.

FIGS. 72B and 72C are high-resolution planar TEM images of the CAAC-OSfilm obtained just after the deposition and the CAAC-OS film subjectedto the heat treatment at 450° C., respectively. Comparison between FIGS.72B and 72C shows that the CAAC-OS film subjected to the heat treatmentat 450° C. has more uniform film quality. That is, the heat treatment athigh temperatures improves the film quality of the CAAC-OS film.

With such a measurement method, the structure of an oxide semiconductorfilm having a plurality of structures can be analyzed in some cases.

Next, an amorphous oxide semiconductor is described.

The amorphous oxide semiconductor is an oxide semiconductor havingdisordered atomic arrangement and no crystal part and exemplified by anoxide semiconductor which exists in an amorphous state as quartz.

In a high-resolution TEM image of the amorphous oxide semiconductor,crystal parts cannot be found.

When the amorphous oxide semiconductor is subjected to structuralanalysis by an out-of-plane method with an XRD apparatus, a peak whichshows a crystal plane does not appear. A halo pattern is observed whenthe amorphous oxide semiconductor is subjected to electron diffraction.Furthermore, a spot is not observed and a halo pattern appears when theamorphous oxide semiconductor is subjected to nanobeam electrondiffraction.

There are various understandings of an amorphous structure. For example,a structure whose atomic arrangement does not have ordering at all iscalled a completely amorphous structure. Meanwhile, a structure whichhas ordering until the nearest neighbor atomic distance or thesecond-nearest neighbor atomic distance but does not have long-rangeordering is also called an amorphous structure. Therefore, the strictestdefinition does not permit an oxide semiconductor to be called anamorphous oxide semiconductor as long as even a negligible degree ofordering is present in an atomic arrangement. At least an oxidesemiconductor having long-term ordering cannot be called an amorphousoxide semiconductor. Accordingly, because of the presence of crystalpart, for example, a CAAC-OS and an nc-OS cannot be called an amorphousoxide semiconductor or a completely amorphous oxide semiconductor.

Note that an oxide semiconductor may have a structure having physicalproperties intermediate between the nc-OS and the amorphous oxidesemiconductor. The oxide semiconductor having such a structure isspecifically referred to as an amorphous-like oxide semiconductor(a-like OS).

In a high-resolution TEM image of the a-like OS, a void may be observed.Furthermore, in the high-resolution TEM image, there are a region wherea crystal part is clearly observed and a region where a crystal part isnot observed.

A difference in effect of electron irradiation between structures of anoxide semiconductor is described below.

An a-like OS, an nc-OS, and a CAAC-OS are prepared. Each of the samplesis an In—Ga—Zn oxide.

First, a high-resolution cross-sectional TEM image of each sample isobtained. The high-resolution cross-sectional TEM images show that allthe samples have crystal parts.

Then, the size of the crystal part of each sample is measured. FIG. 77shows the change in the average size of crystal parts (at 22 points to45 points) in each sample. Sample A has the a-like OS, Sample B has thenc-OS, and Sample C has the CAAC-OS. FIG. 77 indicates that the crystalpart size in the a-like OS increases with an increase in the cumulativeelectron dose. Specifically, as shown by (1) in FIG. 77, a crystal partof approximately 1.2 nm at the start of TEM observation grows to a sizeof approximately 2.6 nm at a cumulative electron dose of 4.2×10⁸ e⁻/nm².In contrast, the crystal part size in the nc-OS and the CAAC-OS showslittle change from the start of electron irradiation to a cumulativeelectron dose of 4.2×10⁸ e⁻/nm² regardless of the cumulative electrondose. Specifically, as shown by (2) in FIG. 77, the average crystal sizeis approximately 1.4 nm regardless of the observation time by TEM.Furthermore, as shown by (3) in FIG. 77, the average crystal size isapproximately 2.1 nm regardless of the observation time by TEM.

In this manner, growth of the crystal part occurs due to thecrystallization of the a-like OS, which is induced by a slight amount ofelectron beam employed in the TEM observation. In contrast, in the nc-OSand the CAAC-OS that have good quality, crystallization hardly occurs bya slight amount of electron beam used for TEM observation.

Note hat the crystal part size in the a-like OS and the nc-OS can bemeasured using high-resolution TEM images. For example, an InGaZnO₄crystal has a layered structure in which two Ga—Zn—O layers are includedbetween In—O layers. A unit cell of the InGaZnO₄ crystal has a structurein which nine layers including three In—O layers and six Ga—Zn—O layersare stacked in the c-axis direction. Accordingly, the distance betweenthe adjacent layers is equivalent to the lattice spacing on the (009)plane (also referred to as d value). The value is calculated to be 0.29nm from crystal structural analysis. Thus, focusing on lattice fringesin the high-resolution TEM image, each of lattice fringes in which thelattice spacing therebetween is greater than or equal to 0.28 nm andless than or equal to 0.30 nm corresponds to the a-b plane of theInGaZnO₄ crystal.

Furthermore, the density of an oxide semiconductor varies depending onthe structure in some cases. For example, when the composition of anoxide semiconductor is determined, the structure of the oxidesemiconductor can be expected by comparing the density of the oxidesemiconductor with the density of a single crystal oxide semiconductorhaving the same composition as the oxide semiconductor. For example, thedensity of the a-like OS is higher than or equal to 78.6% and lower than92.3% of the density of the single crystal oxide semiconductor havingthe same composition. For example, the density of each of the nc-OS andthe CAAC-OS is higher than or equal to 92.3% and lower than 100% of thedensity of the single crystal oxide semiconductor having the samecomposition. Note that it is difficult to deposit an oxide semiconductorhaving a density of lower than 78% of the density of the single crystaloxide semiconductor.

Specific examples of the above description are given. For example, inthe case of an oxide semiconductor having an atomic ratio ofIn:Ga:Zn=1:1:1, the density of single crystal InGaZnO₄ with arhombohedral crystal structure is 6.357 g/cm³. Accordingly, in the caseof the oxide semiconductor having an atomic ratio of In:Ga:Zn=1;1:1, thedensity of the a-like OS is higher than or equal to 5.0 g/cm³ and lowerthan 5.9 g/cm³. For example, in the case of the oxide semiconductorhaving an atomic ratio of In:Ga:Zn=1:1:1, the density of each of thenc-OS and the CAAC-OS is higher than or equal to 5.9 g/cm³ and lowerthan 6.3 g/cm³.

Note that there is a possibility that an oxide semiconductor having acertain composition cannot exist in a single crystal structure. In thatcase, single crystal oxide semiconductors with different compositionsare combined at an adequate ratio, which makes it possible to calculatedensity equivalent to that of a single crystal oxide semiconductor withthe desired composition. The density of a single crystal oxidesemiconductor having the desired composition can be calculated using aweighted average according to the combination ratio of the singlecrystal oxide semiconductors with different compositions. Note that itis preferable to use as few kinds of single crystal oxide semiconductorsas possible to calculate the density.

Note that an oxide semiconductor may be a stacked film including two ormore films of an amorphous oxide semiconductor, an a-like OS, amicrocrystalline oxide semiconductor, and a CAAC-OS, for example.

An oxide semiconductor having a low impurity concentration and a lowdensity of defect states (a small number of oxygen vacancies) can havelow carrier density. Therefore, such an oxide semiconductor is referredto as a highly purified intrinsic or substantially highly purifiedintrinsic oxide semiconductor. A CAAC-OS and an nc-OS have a lowimpurity concentration and a low density of defect states as compared toan a-like OS and an amorphous oxide semiconductor. That is, a CAAC-OSand an nc-OS are likely to be highly purified intrinsic or substantiallyhighly purified intrinsic oxide semiconductors. Thus, a transistorincluding a CAAC-OS or an nc-OS rarely has negative threshold voltage(is rarely normally on). The highly purified intrinsic or substantiallyhighly purified intrinsic oxide semiconductor has few carrier traps.Therefore, a transistor including a CAAC-OS or an nc-OS has smallvariation in electrical characteristics and high reliability. Anelectric charge trapped by the carrier traps in the oxide semiconductortakes a long time to be released. The trapped electric charge may behavelike a fixed electric charge. Thus, the transistor including the oxidesemiconductor, which has a high impurity concentration and a highdensity of defect states, might have unstable electricalcharacteristics.

<Deposition Model>

Examples of deposition models of a CAAC-OS and an nc-OS are describedbelow.

FIG. 78A is a schematic view of the inside of a deposition chamber wherea CAAC-OS is deposited by a sputtering method.

A target 5130 is attached to a backing plate. A plurality of magnets isprovided to face the target 5130 with the backing plate positionedtherebetween. The plurality of magnets generates a magnetic field. Theabove description on the deposition chamber is referred to for thelayout and structure of magnets. A sputtering method in which thedisposition rate is increased by utilizing a magnetic field of magnetsis referred to as a magnetron sputtering method.

The target 5130 has a polycrystalline structure in which a cleavageplane exists in at least one crystal grain.

A cleavage plane of the target 5130 including an In—Ga—Zn oxide isdescribed as an example. FIG. 79A shows a structure of an InGaZnO₄crystal included in the target 5130. Note that FIG. 79A shows astructure of the case where the InGaZnO₄ crystal is observed from adirection parallel to the b-axis when the c-axis is in an upwarddirection.

FIG. 79A indicates that oxygen atoms in a Ga—Zn—O layer are positionedclose to those in an adjacent Ga—Zn—O layer. The oxygen atoms havenegative charge, whereby the two Ga—Zn—O layers repel each other. As aresult, the InGaZnO₄ crystal has a cleavage plane between the twoadjacent Ga—Zn—O layers.

The substrate 5120 is placed to face the target 5130, and the distanced(also referred to as a target-substrate distance (T-S distance)) isgreater than or equal to 0.01 m and less than or equal to 1 m,preferably greater than or equal to 0.02 m and less than or equal to 0.5m. The deposition chamber is mostly filled with a deposition gas (e.g.,an oxygen gas, an argon gas, or a mixed gas containing oxygen at 5 vol %or higher) and the pressure in the deposition chamber is controlled tobe higher than or equal to 0.01 Pa and lower than or equal to 100 Pa,preferably higher than or equal to 0.1 Pa and lower than or equal to 10Pa. Here, discharge starts by application of a voltage at a certainvalue or higher to the target 5130, and plasma is observed. The magneticfield forms a high-density plasma region in the vicinity of the target5130. In the high-density plasma region, the deposition gas is ionized,so that an ion 5101 is generated. Examples of the ion 5101 include anoxygen cation (O⁺) and an argon cation (Ar⁺).

The ion 5101 is accelerated toward the target 5130 side by an electricfield, and then the ion 5101 collides with the target 5130. At thistime, a pellet 5100 a and a pellet 5100 b, which are flat-plate-like(pellet-like) sputtered particles, are separated and sputtered from thecleavage plane. Note that structures of the pellet 5100 a and the pellet5100 b may be distorted by an impact of collision of the ion 5101.

The pellet 5100 a is a flat-plate-like (pellet-like) sputtered particlehaving a triangle plane, e.g., regular triangle plane. The pellet 5100 bis a flat-plate-like (pellet-like) sputtered particle having a hexagonplane, e.g., regular hexagon plane. Note that flat-plate-like(pellet-like) sputtered particles such as the pellet 5100 a and thepellet 5100 b are collectively called pellets 5100 (see FIG. 73D). Theshape of a flat plane of the pellet 5100 is not limited to a triangle ora hexagon. For example, the flat plane may have a shape formed bycombining two or more triangles. For example, a quadrangle (e.g.,rhombus) may be formed by combining two triangles (e.g., regulartriangles).

The thickness of the pellet 5100 is determined depending on the kind ofdeposition gas and the like. The thicknesses of the pellets 5100 arepreferably uniform; the reason for this is described later. In addition,the sputtered particle preferably has a pellet shape with a smallthickness as compared to a dice shape with a large thickness. Forexample, the thickness of the pellet 5100 is greater than or equal to0.4 nm and less than or equal to 1 nm, preferably greater than or equalto 0.6 nm and less than or equal to 0.8 nm. In addition, for example,the width of the pellet 5100 is greater than or equal to 1 nm and lessthan or equal to 3 nm, preferably greater than or equal to 1.2 nm andless than or equal to 2.5 nm. The pellet 5100 corresponds to the initialnucleus in the description of (1) in FIG. 77. For example, in the casewhere the ion 5101 collides with the target 5130 including an In—Ga—Znoxide, the pellet 5100 that includes three layers of a Ga—Zn—O layer, anIn—O layer, and a Ga—Zn—0 layer as shown in FIG. 79B is ejected. Notethat FIG. 79C shows the structure of the pellet 5100 observed from adirection parallel to the c-axis. Therefore, the pellet 5100 has ananometer-sized sandwich structure including two Ga—Zn—O layers and anIn—O layer.

The pellet 5100 may receive a charge when passing through the plasma, sothat side surfaces thereof are negatively or positively charged. Thepellet 5100 includes an oxygen atom on its side surface, and the oxygenatom may be negatively charged. In this manner, when the side surfacesare charged with the same polarity, charges repel each other, andaccordingly, the pellet 5100 can maintain a flat-plate shape. In thecase where a CAAC-OS is an In—Ga—Zn oxide, there is a possibility thatan oxygen atom, bonded to an indium atom is negatively charged. There isanother possibility that an oxygen atom bonded to an indium atom, agallium atom, or a zinc atom is negatively charged. In addition, thepellet 5100 may grow by being bonded with an indium atom, a galliumatom, a zinc atom, an oxygen atom, or the like when passing throughplasma. This is a cause of a difference in size between (2) and (1) inFIG. 77. Here, in the case where the temperature of the substrate 5120is at around room temperature, the pellet 5100 does not grow anymore;thus, an nc-OS is formed (see FIG. 78B). An nc-OS can be deposited whenthe substrate 5120 has a large size because a temperature at which thedeposition of an nc-OS is carried out is approximately room temperature.Note that in order that the pellet 5100 grows in plasma, it is effectiveto increase deposition power in sputtering. High deposition power canstabilize the structure of the pellet 5100.

As shown in FIGS. 78A and 78B, the pellet 5100 flies like a kite inplasma and flutters up to the substrate 5120. Since the pellets 5100 arecharged, when the pellet 5100 gets close to a region where anotherpellet 5100 has already been deposited, repulsion is generated. Here,above the substrate 5120, a magnetic field in a direction parallel tothe top surface of the substrate 5120 (also referred to as a horizontalmagnetic field) is generated. A potential difference is given betweenthe substrate 5120 and the target 5130, and accordingly, current flowsfrom the substrate 5120 toward the target 5130. Thus, the pellet 5100 isgiven a force (Lorentz force) on the top surface of the substrate 5120by an effect of the magnetic field and the current. This is explainablewith Fleming's left-hand rule.

The mass of the pellet 5100 is larger than that of an atom. Therefore,to move the pellet 5100 over the top surface of the substrate 5120, itis important to apply some force to the pellet 5100 from the outside.One kind of force may be force which is generated by the action of amagnetic field and current. In order to increase a force applied to thepellet 5100, it is preferable to provide, on the top surface, a regionwhere the magnetic field in a direction parallel to the top surface ofthe substrate 5120 is 10 G or higher, preferably 20 G or higher, furtherpreferably 30 G or higher, still further preferably 50 G or higher.Alternatively, it is preferable to provide, on the top surface, a regionwhere the magnetic field in a direction parallel to the top surface ofthe substrate 5120 is 1.5 times or higher, preferably twice or higher,further preferably 3 times or higher, still further preferably 5 timesor higher as high as the magnetic field in a direction perpendicular tothe top surface of the substrate 5120.

At this time, the magnets and/or the substrate 5120 are moved or rotatedrelatively, whereby the direction of the horizontal magnetic field onthe top surface of the substrate 5120 continues to change. Therefore,the pellet 5100 can be moved in various directions on the top surface ofthe substrate 5120 by receiving forces in various directions.

Furthermore, as shown in FIG. 78A, when the substrate 5120 is heated,resistance between the pellet 5100 and the substrate 5120 due tofriction or the like is low. As a result, the pellet 5100 glides abovethe top surface of the substrate 5120. The glide of the pellet 5100 iscaused in a state where its flat plane faces the substrate 5120. Then,when the pellet 5100 reaches the side surface of another pellet 5100that has been already deposited, the side surfaces of the pellets 5100are bonded. At this time, the oxygen atom on the side surface of thepellet 5100 is released. With the released oxygen atom, oxygen vacanciesin a CAAC-OS might be filled; thus, the CAAC-OS has a low density ofdefect states. Note that the temperature of the top surface of thesubstrate 5120 is, for example, higher than or equal to 100° C. andlower than 500° C., higher than or equal to 150° C. and lower than 450°C., or higher than or equal to 170° C. and lower than 400° C. Hence,even when the substrate 5120 has a large size, it is possible to deposita CAAC-OS.

Furthermore, the pellet 5100 is heated on the substrate 5120, wherebyatoms are rearranged, and the structure distortion caused by thecollision of the ion 5101 can be reduced. The pellet 5100 whosestructure distortion is reduced is substantially single crystal. Evenwhen the pellets 5100 are heated after being bonded, expansion andcontraction of the pellet 5100 itself hardly occur, which is caused byturning the pellet 5100 into substantially single crystal. Thus,formation of defects such as a grain boundary due to expansion of aspace between the pellets 5100 can be prevented, and accordingly,generation of crevasses can be prevented.

The CAAC-OS does not have a structure like a board of a single crystaloxide semiconductor but has arrangement with a group of pellets 5100(nanocrystals) like stacked bricks or blocks. Furthermore, a grainboundary does not exist therebetween. Therefore, even when deformationsuch as shrink occurs in the CAAC-OS owing to heating during deposition,heating or bending after deposition, it is possible to relieve localstress or release distortion. Therefore, this structure is suitable fora flexible semiconductor device. Note that the nc-OS has arrangement inwhich pellets 5100 (nanocrystals) are randomly stacked.

When the target is sputtered with an ion, in addition to the pellets,zinc oxide or the like may be ejected. The zinc oxide is lighter thanthe pellet and thus reaches the top surface of the substrate 5120 beforethe pellet. As a result, the zinc oxide forms a zinc oxide layer 5102with a thickness greater than or equal to 0.1 nm and less than or equalto 10 nm, greater than or equal to 0.2 nm and less than or equal to 5nm, or greater than or equal to 0.5 nm and less than or equal to 2 nm.FIGS. 80A to 80D are cross-sectional schematic views.

As illustrated in FIG. 80A, a pellet 5105 a and a pellet 5105 b aredeposited over the zinc oxide layer 5102. Here, side surfaces of thepellet 5105 a and the pellet 5105 b are in contact with each other. Inaddition, a pellet 5105 c is deposited over the pellet 5105 b, and thenglides over the pellet 5105 b. Furthermore, a plurality of particles5103 ejected from the target together with the zinc oxide iscrystallized by heating of the substrate 5120 to form a region 5105 a 1on another side surface of the pellet 5105 a. Note that the plurality ofparticles 5103 may contain oxygen, zinc, indium, gallium, or the like.

Then, as illustrated in FIG. 80B, the region 5105 a 1 grows to part ofthe pellet 5105 a to form a pellet 5105 a 2. In addition, a side surfaceof the pellet 5105 c is in contact with another side surface of thepellet 5105 b.

Next, as illustrated in FIG. 80C, a pellet 5105 d is deposited over thepellet 5105 a 2 and the pellet 5105 b, and then glides over the pellet5105 a 2 and the pellet 5105 b. Furthermore, a pellet 5105 e glidestoward another side surface of the pellet 5105 c over the zinc oxidelayer 5102.

Then, as illustrated in FIG, 80D, the pellet 5105 d is placed so that aside surface of the pellet 5105 d is in contact with a side surface ofthe pellet 5105 a 2. Furthermore, a side surface of the pellet 5105 e isin contact with another side surface of the pellet 5105 c. A pluralityof particles 5103 ejected from the target together with the zinc oxideis crystallized by heating of the substrate 5120 to form a region 5105 d1 on another side surface of the pellet 5105 d.

As described above, deposited pellets are placed to be in contact witheach other and then crystal growth is caused at side surfaces of thepellets, whereby a CAAC-OS is formed over the substrate 5120. Therefore,each pellet of the CAAC-OS is larger than that of the nc-OS. Thiscorresponds to a difference in size between (3) and (2) in FIG. 77.

When spaces between pellets 5100 are extremely small, the pellets mayform a large pellet. The large pellet has a single crystal structure.For example, the size of the large pellet may be greater than or equalto 10 nm and less than or equal to 200 nm, greater than or equal to 15nm and less than or equal to 100 nm, or greater than or equal to 20 nmand less than or equal to 50 nm, when seen from the above. Therefore,when a channel formation region of a transistor is smaller than thelarge pellet, the region having a single crystal structure can be usedas the channel formation region. Furthermore, when the size of thepellet is increased, the region having a single crystal structure can beused as the channel formation region, the source region, and the drainregion of the transistor.

In this manner, when the channel formation region or the like of thetransistor is formed in a region having a single crystal structure, thefrequency characteristics of the transistor can be increased in somecases.

As shown in such a model, the pellets 5100 are considered to bedeposited on the substrate 5120. Thus, a CAAC-OS can be deposited evenWhen a formation surface does not have a crystal structure, which isdifferent from film deposition by epitaxial growth. For example, evenwhen the top surface (formation surface) of the substrate 5120 has anamorphous structure (e.g., the top surface is formed of amorphoussilicon oxide), a CAAC-OS can be formed.

In addition, it is found that in formation of the CAAC-OS, the pellets5100 are arranged in accordance with the top surface shape of thesubstrate 5120 that is the formation surface even when the formationsurface has unevenness. For example, in the case where the top surfaceof the substrate 5120 is fiat at the atomic level, the pellets 5100 arearranged so that flat planes parallel to the a-b plane face downwardsthus, a layer with a uniform thickness, flatness, and high crystallinityis formed. By stacking n layers (n is a natural number), the CAAC-OS canbe obtained.

In the case where the top surface of the substrate 5120 has unevenness,a CAAC-OS in which n layers is a natural number) in each of which thepellets 5100 are arranged along the unevenness are stacked is formed.Since the substrate 5120 has unevenness, a gap is easily generatedbetween the pellets 5100 in the CAAC-OS in some cases. Note that owingto intermolecular force, the pellets 5100 are arranged so that a gapbetween the pellets is as small as possible even on the unevennesssurface. Therefore, even when the formation surface has unevenness, aCAAC-OS with high crystallinity can be obtained.

As a result, laser crystallization is not needed for formation of aCAAC-OS, and a uniform film can be formed even over a large-sized glasssubstrate or the like.

Since a CAAC-OS is deposited in accordance with such a model, thesputtered particle preferably has a pellet shape with a small thickness.Note that when the sputtered particles have a dice shape with a largethickness, planes facing the substrate 5120 vary; thus, the thicknessesand orientations of the crystals cannot be uniform in some cases.

According to the deposition model described above, a CAAC-OS with highcrystallinity can be formed even on a formation surface with anamorphous structure.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

(Embodiment 6)

In this embodiment, a structural example of a display panel of oneembodiment of the present invention is described.

<Structural Example>

FIG. 42A is a top view of the display panel of one embodiment of thepresent invention. FIG. 42B is a circuit diagram illustrating a pixelcircuit that can be used in the case where a liquid crystal element isused in a pixel in the display panel of one embodiment of the presentinvention. FIG. 42C is a circuit diagram illustrating a pixel circuitthat can be used in the case where an organic EL element is used in apixel in the display panel of one embodiment of the present invention.

The transistor in the pixel portion can be formed in accordance with theabove embodiments. Further, the transistor can easily be an n-channeltransistor, and thus, part of a driver circuit that can be formed usingan n-channel transistor in the driver circuit is formed over the samesubstrate as the transistor of the pixel portion. With the use of any ofthe transistors described in the above embodiments for the pixel portionor the driver circuit in this manner, a highly reliable display devicecan be provided.

FIG. 42A illustrates an example of a block diagram of an active matrixdisplay device. A pixel portion 901, a first scan line driver circuit902, a second scan line driver circuit 903, and a signal line drivercircuit 904 are provided over a substrate 900 in the display device. Inthe pixel portion 901, a plurality of signal lines extended from thesignal line driver circuit 904 are arranged, and a plurality of scanlines extended from the first scan line driver circuit 902 and thesecond scan line driver circuit 903 are arranged. Pixels each includinga display element are provided in matrix in respective regions in eachof which the scan line and the signal line intersect with each other.The substrate 900 of the display device is connected to a timing controlcircuit (also referred to as controller or control IC) through aconnection portion such as a flexible printed circuit (FPC).

In FIG. 42A, the first scan line driver circuit 902, the second scanline driver circuit 903, and the signal line driver circuit 904 areformed over the same substrate 900 as the pixel portion 901.Accordingly, the number of components provided outside, such as a drivercircuit, is reduced, so that a reduction in cost can be achieved.Further, if the driver circuit is provided outside the substrate 900,wirings would need to be extended and the number of wiring connectionswould increase. However, by providing the driver circuit over thesubstrate 900, the number of wiring connections can be reduced and thereliability or yield can be improved.

<Liquid Crystal Panel>

FIG. 42B illustrates an example of a circuit configuration of the pixel.Here, a pixel circuit that can be used in a pixel of a VA liquid crystaldisplay panel is illustrated.

This pixel circuit can be used in a structure in which one pixelincludes a plurality of pixel electrodes. The pixel electrodes areconnected to different transistors, and the transistors can be drivenwith different gate signals. Accordingly, signals applied to individualpixel electrodes in a multi-domain pixel can be controlledindependently.

A gate wiring 912 of a transistor 916 and a gate wiring 913 of atransistor 917 are separated so that different gate signals can be giventhereto. In contrast, a source or drain electrode 914 serving as a dataline is used in common for the transistors 916 and 917. Any of thetransistors described in the above embodiments can be used asappropriate as each of the transistors 916 and 917. In this way, ahighly reliable liquid crystal display panel can be provided.

The shapes of a first pixel electrode electrically connected to thetransistor 916 and a second pixel electrode electrically connected tothe transistor 917 are described. The first pixel electrode and thesecond pixel electrode are separated by a slit. The first pixelelectrode has a V-shape and the second pixel electrode is provided so asto surround the first pixel electrode.

A gate electrode of the transistor 916 is connected to the gate wiring912, and a gate electrode of the transistor 917 is connected to the gatewiring 913. When different gate signals are supplied to the gate wiring912 and the gate wiring 913, operation timings of the transistor 916 andthe transistor 917 can be varied. As a result, alignment of liquidcrystals can be controlled.

Further, a storage capacitor may be formed using a capacitor wiring 910,a gate insulating film serving as a dielectric, and a capacitorelectrode electrically connected to the first pixel electrode or thesecond pixel electrode.

The multi-domain pixel includes a first liquid crystal element 918 and asecond liquid crystal element 919. The first liquid crystal element 918includes the first pixel electrode, a counter electrode, and a liquidcrystal layer therebetween. The second liquid crystal element 919includes the second pixel electrode, a counter electrode, and a liquidcrystal layer therebetween.

Note that a pixel circuit of the present invention is not limited tothat shown in FIG. 42B. For example, a switch, a resistor, a capacitor,a transistor, a sensor, a logic circuit, or the like may be added to thepixel illustrated in FIG. 42B.

<Organic EL Panel>

FIG. 42C illustrates another example of a circuit configuration of thepixel. Here, a pixel structure of a display panel using an organic ELelement is illustrated.

In an organic EL element, by application of voltage to a light-emittingelement, electrons are injected from one of a pair of electrodes andholes are injected from the other of the pair of electrodes, into alayer containing a light-emitting organic compound; thus, current flows.The electrons and holes are recombined, and thus, the light-emittingorganic compound is excited. The light-emitting organic compound returnsto a ground state from the excited state, thereby emitting light. Basedon such a mechanism, such a light-emitting element is referred to as acurrent-excitation type light-emitting element.

FIG. 42C illustrates an example of a pixel circuit that can be used.Here, an example in which an n-channel transistor is used in the pixelis shown. Further, digital time grayscale driving can be employed forthe pixel circuit.

The configuration of the pixel circuit that can be used and operation ofa pixel employing digital time grayscale driving are described.

A pixel 920 includes a switching transistor 921, a driving transistor922, a light-emitting element 924, and a capacitor 923. A gate electrodeof the switching transistor 921 is connected to a scan line 926. A firstelectrode (one of a source electrode and a drain electrode) of theswitching transistor 921 is connected to a signal line 925. A secondelectrode (the other of the source electrode and the drain electrode) ofthe switching transistor 921 is connected to a gate electrode of thedriving transistor 922. The gate electrode of the driving transistor 922is connected to a power supply line 927 through the capacitor 923, afirst electrode of the driving transistor 922 is connected to the powersupply line 927, and a second electrode of the driving transistor 922 isconnected to a first electrode (pixel electrode) of the light-emittingelement 924. A second electrode of the light-emitting element 924corresponds to a common electrode 928. The common electrode 928 iselectrically connected to a common potential line formed over the samesubstrate as the common electrode 928.

As the switching transistor 921 and the driving transistor 922, any ofthe transistors described in the above embodiments can be used asappropriate. In this way, a highly reliable organic EL display panel canbe provided.

The potential of the second electrode (the common electrode 928) of thelight-emitting element 924 is set to be a low power supply potential.Note that the low power supply potential is lower than a high powersupply potential supplied to the power supply line 927. For example, thelow power supply potential can be CAD, 0 V, or the like. The high powersupply potential and the low power supply potential are set to be higherthan or equal to the forward threshold voltage of the light-emittingelement 924, and the difference between the potentials is applied to thelight-emitting element 924, whereby current is supplied to thelight-emitting element 924, leading to light emission. The forwardvoltage of the light-emitting element 924 refers to a voltage at which adesired luminance is obtained, and at least includes a forward thresholdvoltage.

Note that gate capacitance of the driving transistor 922 may be used asa substitute for the capacitor 923, so that the capacitor 923 can beomitted. The gate capacitance of the driving transistor 922 may beformed between the semiconductor film and the gate electrode.

Next, a signal input to the driving transistor 922 is described. For avoltage-input voltage driving method, a video signal for turning on oroff the driving transistor 922 without fail is input to the drivingtransistor 922. In order for the driving transistor 922 to operate in asubthreshold region, voltage higher than the voltage of the power supplyline 927 is applied to the gate electrode of the driving transistor 922.Voltage higher than or equal to voltage that is the sum of power supplyline voltage and the threshold voltage V_(th) of the driving transistor922 is applied to the signal line 925.

In the case where analog grayscale driving is performed, voltage higherthan or equal to voltage that is the sum of the forward voltage of thelight-emitting element 924 and the threshold voltage V_(th) of thedriving transistor 922 is applied to the gate electrode of the drivingtransistor 922. A video signal by which the driving transistor 922 isoperated in a saturation region is input, so that current is supplied tothe light-emitting element 924. In order for the driving transistor 922to operate in a saturation region, the potential of the power supplyline 927 is set higher than the gate potential of the driving transistor922. When an analog video signal is used, current corresponding to thevideo signal can be supplied to the light-emitting element 924 andanalog grayscale driving can be performed.

Note that the configuration of the pixel circuit is not limited to thatshown in FIG. 42C. For example, a switch, a resistor, a capacitor, asensor, a transistor, a logic circuit, or the like may be added to thepixel circuit illustrated in FIG. 42C.

In the case where the transistor described in the above embodiments isused for the circuit shown in FIGS. 42A to 42C, the source electrode(the first electrode) is electrically connected to the low potentialside and the drain electrode (the second electrode) is electricallyconnected to the high potential side. Further, the potential of thefirst gate electrode (and the third gate electrode) may be controlled bya control circuit or the like, and a potential lower than the potentialapplied to the source electrode may be input to the second gateelectrode through a wiring that is not illustrated.

In this specification and the like, for example, a display element, adisplay device which is a device including a display element, alight-emitting element, and a light-emitting device which is a deviceincluding a light-emitting element can employ a variety of modes or caninclude a variety of elements. Examples of a display element, a displaydevice, a light-emitting element, or a light-emitting device include adisplay medium whose contrast, luminance, reflectance, transmittance, orthe like is changed by electromagnetic action, such as anelectroluminescence (EL) element (e.g., an EL element including organicand inorganic materials, an organic EL element, or an inorganic ELelement), an LED (e.g., a white LED, a red LED, a green LED, or a blueLED), a transistor (a transistor that emits light depending on current),an electron emitter, a liquid crystal element, electronic ink, anelectrophoretic element, a grating light valve (GLV), a plasma displaypanel (PDP), a display element using micro electro mechanical system(MEMS), a digital micromirror device (DMD), a digital micro shutter(DMS), MIRASOL (registered trademark), an interferometric modulatordisplay (IMOD) element, a MEMS shutter display element, anoptical-interference-type MEMS display element, an electrowettingelement, a piezoelectric ceramic display, or a carbon nanotube. Notethat examples of a display device having an EL element include an ELdisplay. Examples of a display device having an electron emitter includea field emission display (FED) and an SED-type flat panel display (SED:surface-conduction electron-emitter display). Examples of a displaydevice having a liquid crystal element include a liquid crystal display(e.g., a transmissive liquid crystal display, a transflective liquidcrystal display, a reflective liquid crystal display, a direct-viewliquid crystal display, or a projection liquid crystal display).Examples of a display device using electronic ink or electrophoreticelements include electronic paper.

FIG. 43 illustrates an example in which the transistor illustrated inFIG. 1B is provided with a liquid crystal element. The liquid crystalelement includes a pixel electrode 80, a liquid crystal layer 83, and acommon electrode 82. The common electrode 82 is provided on a substrate81. For another example, FIG. 44 illustrates an example in which thetransistor illustrated in FIG. 5A is provided with a light-emittingelement. An insulating film 84 is provided over the electrodes 19 and20. The pixel electrode 80 is provided over the insulating film 84, andan insulating film 85 is provided over the pixel electrode 80. Thelight-emitting element includes the pixel electrode 80, a light-emittinglayer 86, and the common electrode 82. A variety of display devices canbe formed by combining a variety of display elements and transistorswith a variety of structures as described above.

This embodiment can be combined with any of the other embodimentsdisclosed in this specification as appropriate.

(Embodiment 7)

In this embodiment, a display module and electronic devices that can beformed using a semiconductor device of one embodiment of the presentinvention are described.

In a display module 8000 illustrated in FIG. 45, a touch panel 8004connected to an FPC 8003, a display panel 8006 connected to an FPC 8005,a backlight unit 8007, a frame 8009, a printed board 8010, and a battery8011 are provided between an upper cover 8001 and a lower cover 8002.Note that the backlight unit 8007, the battery 8011, the touch panel8004, and the like are not provided in some cases.

The semiconductor device of one embodiment of the present invention canbe used for, for example, the display panel 8006.

The shapes and sizes of the upper cover 8001 and the lower cover 8002can be changed as appropriate in accordance with the sizes of the touchpanel 8004 and the display panel 8006.

The touch panel 8004 can be a resistive touch panel or a capacitivetouch panel and can be formed to overlap with the display panel 8006. Acounter substrate (sealing substrate) of the display panel 8006 can havea touch panel function. A photosensor may be provided in each pixel ofthe display panel 8006 to form an optical touch panel. An electrode fora touch sensor may be provided in each pixel of the display panel 8006so that a capacitive touch panel is obtained.

The backlight unit 8007 includes a light source 8008. The light source8008 may be provided at an end portion of the backlight unit 8007 and alight diffusing plate may be used.

The frame 8009 protects the display panel 8006 and also functions as anelectromagnetic shield for blocking electromagnetic waves generated bythe operation of the printed board 8010. The frame 8009 may function asa radiator plate.

The printed board 8010 is provided with a power supply circuit and asignal processing circuit for outputting a video signal and a clocksignal. As a power source for supplying power to the power supplycircuit, an external commercial power source or a power source using thebattery 8011 provided separately may be used. The battery 8011 can beomitted in the case of using a commercial power source.

The display module 8000 may be additionally provided with a member suchas a polarizing plate, a retardation plate, or a prism sheet.

FIGS. 46A to 46D are external views of electronic devices each includingthe semiconductor device of one embodiment of the present invention.

Examples of electronic devices are a television set (also referred to asa television or a television receiver), a monitor of a computer or thelike, a camera such as a digital camera or a digital video camera, adigital photo frame, a mobile phone handset (also referred to as amobile phone or a mobile phone device), a portable game machine, aportable information terminal, an audio reproducing device, alarge-sized game machine such as a pachinko machine, and the like.

FIG. 46A illustrates a portable information terminal including a mainbody 1001, a housing 1002, display portions 1003 a and 1003 b, and thelike. The display portion 1003 b is a touch panel. By touching akeyboard button 1004 displayed on the display portion 1003 b, a screencan be operated, and text can be input. It is needless to say that thedisplay portion 1003 a may be a touch panel. A liquid crystal panel oran organic light-emitting panel is manufactured by using any of thetransistors described in the above embodiments as a switching elementand used in the display portion 1003 a or 1003 b, whereby a highlyreliable portable information terminal can be provided.

The portable information terminal illustrated in FIG. 46A has a functionof displaying various kinds of data (e.g., a still image, a movingimage, and a text image) on the display portion, a function ofdisplaying a calendar, a date, the time, or the like on the displayportion, a function of operating or editing the data displayed on thedisplay portion, a function of controlling processing by various kindsof software (programs), and the like. Furthermore, an externalconnection terminal (an earphone terminal, a USB terminal, or the like),a recording medium insertion portion, and the like may be provided onthe back surface or the side surface of the housing.

The portable information terminal illustrated in FIG. 46A may transmitand receive data wirelessly. Through wireless communication, desiredbook data or the like can be purchased and downloaded from an e-bookserver.

FIG. 46B illustrates a portable music player including, in a main body1021, a display portion 1023, a fixing portion 1022 with which theportable music player can be worn on the ear, a speaker, an operationbutton 1024, an external memory slot 1025, and the like. A liquidcrystal panel or an organic light-emitting panel is fabricated using anyof the transistors described in the above embodiments as a switchingelement, and used in the display portion 1023, whereby a highly reliableportable music player can be provided.

Furthermore, when the portable music player illustrated in FIG. 46B hasan antenna, a microphone function, or a wireless communication functionand is used with a mobile phone, a user can talk on the phone wirelesslyin a hands-free way while driving a car or the like.

FIG. 46C illustrates a mobile phone that includes two housings, ahousing 1030 and a housing 1031. The housing 1031 includes a displaypanel 1032, a speaker 1033, a microphone 1034, a pointing device 1036, acamera lens 1037, an external connection terminal 1038, and the like.The housing 1030 is provided with a solar cell 1040 for charging themobile phone, an external memory slot 1041, and the like. In addition,an antenna is incorporated in the housing 1031. Any of the transistorsdescribed in the above embodiments is used in the display panel 1032,whereby a highly reliable mobile phone can be provided.

Further, the display panel 1032 includes a touch panel. A plurality ofoperation keys 1035 that are displayed as images are indicated by dottedlines in FIG. 46C. Note that a boosting circuit by which a voltageoutput from the solar cell 1040 is increased to be sufficiently high foreach circuit is also included.

In the display panel 1032, the direction of display is changed asappropriate depending on the application mode. Further, the mobile phoneis provided with the camera lens 1037 on the same surface as the displaypanel 1032, and thus it can be used as a video phone. The speaker 1033and the microphone 1034 can be used for videophone calls, recording, andplaying sound, etc. as well as voice calls. Moreover, the housings 1030and 1031 in a state where they are opened as illustrated in FIG. 46C canshift, by sliding, to a state where one is lapped over the other.Therefore, the size of the mobile phone can be reduced, which makes themobile phone suitable for being carried around.

The external connection terminal 1038 can be connected to an AC adaptorand a variety of cables such as a USB cable, whereby charging and datacommunication with a personal computer or the like are possible.Further, by inserting a recording medium into the external memory slot1041, a larger amount of data can be stored and moved.

Further, in addition to the above functions, an infrared communicationfunction, a television reception function, or the like may be provided.

FIG. 46D illustrates an example of a television set. In a television set1050, a display portion 1053 is incorporated in a housing 1051. Imagescan be displayed on the display portion 1053. Moreover, a CPU isincorporated in a stand 1055 for supporting the housing 1051. Any of thetransistors described in the above embodiments is used in the displayportion 1053 and the CPU, whereby the television set 1050 can have highreliability.

The television set 1050 can be operated with an operation switch of thehousing 1051 or a separate remote controller. Further, the remotecontroller may be provided with a display portion for displaying dataoutput from the remote controller.

Note that the television set 1050 is provided with a receiver, a modem,and the like. With the use of the receiver, general televisionbroadcasting can be received. Moreover, when the television set isconnected to a communication network with or without wires via themodem, one-way (from a sender to a receiver) or two-way (between asender and a receiver or between receivers) information communicationcan be performed.

Further, the television set 1050 is provided with an external connectionterminal 1054, a storage medium recording and reproducing portion 1052,and an external memory slot. The external connection terminal 1054 canbe connected to various types of cables such as a USB cable, and datacommunication with a personal computer or the like is possible. A diskstorage medium is inserted into the storage medium recording andreproducing portion 1052, and reading data stored in the storage mediumand writing data to the storage medium can be performed. In addition, animage, a video, or the like stored as data in an external memory 1056inserted into the external memory slot can be displayed on the displayportion 1053.

Further, in the case where the off-state leakage current of thetransistor described in the above embodiments is extremely small, whenthe transistor is used in the external memory 1056 or the CPU, thetelevision set 1050 can have high reliability and sufficiently reducedpower consumption.

This embodiment can be combined with any of the other embodimentsdisclosed in this specification as appropriate.

EXAMPLE 1

In this example, evaluation results of an oxide insulating film that canbe used for the transistor included in the semiconductor device of oneembodiment of the present invention are described. Specifically, resultsof evaluating, by TDS analysis, the amounts of nitrogen monoxide,dinitrogen monoxide, nitrogen dioxide, ammonia, water, and nitrogenreleased by heating are described.

<Fabrication Methods of Samples>

In this example, Sample A1, which is an oxide insulating film that canbe used for the transistor of one embodiment of the present invention,and Samples A2 and A3 for comparison were fabricated.

<Sample A1>

Sample A1 was fabricated by forming an oxide insulating film over asilicon wafer by a plasma CVD method under formation conditions that canbe used for at least one of the gate insulating film 15 and theprotective film 21 described in Embodiment 1 (see FIGS. 1A to 1C).

Here, as the oxide insulating film, a 400-nm-thick silicon oxynitridefilm was formed by a plasma CVD method under the conditions where thesilicon wafer was held at a temperature of 220° C., silane at a flowrate of 50 sccm and dinitrogen monoxide at a flow rate of 2000 sccm wereused as a source gas, the pressure in the treatment chamber was 20 Pa,and a high-frequency power of 100 W at 13.56 MHz (1.6×10⁻² W/cm² as thepower density) was supplied to parallel-plate electrodes. Note that theflow ratio of dinitrogen monoxide to silane was 40.

<Sample A2>

For Sample A2, instead of the oxide insulating film of Sample A1, anoxide insulating film was formed under the following conditions.

In Sample A2, as the oxide insulating film, a 400-nm-thick siliconoxynitride film was formed by a plasma CVD method under the conditionswhere the silicon wafer was held at a temperature of 220° C., silane ata flow rate of 30 sccm and dinitrogen monoxide at a flow rate of 4000sccm were used as a source gas, the pressure in the treatment chamberwas 40 Pa, and a high-frequency power of 150 W at 13.56 MHz (8.0×10⁻²W/cm² as the power density) was supplied to parallel-plate electrodes.Note that the flow ratio of dinitrogen monoxide to silane was 133.

<Sample A3>

For Sample A3, instead of the oxide insulating film of Sample A1, anoxide insulating film was formed under the following conditions.

In Sample A3, as the oxide insulating film, a 100-nm-thick silicon oxidefilm was formed by a sputtering method under the conditions where thesilicon wafer was held at a temperature of 100° C., a silicon target wasused, oxygen at a flow rate of 50 sccm was used as a sputtering gas, thepressure in the treatment chamber was 0.5 Pa, and a high-frequency powerof 6 kW was supplied to parallel-plate electrodes.

<TDS Analysis>

TDS analyses were performed on Samples A1 to A3. In each sample, a stageon which the sample is mounted was heated at higher than or equal to 55°C. and lower than or equal to 997° C. The amounts of gas having amass-to-charge ratio m/z of 30 (nitrogen monoxide), gas having amass-to-charge ratio m/z of 44 (dinitrogen monoxide), and gas having amass-to-charge ratio m/z of 46 (nitrogen dioxide) released from SamplesA1 to A3 are shown in FIGS. 47A, 47B, and 47C, respectively. Inaddition, the amounts of gas having a mass-to-charge ratio m/z of 17(ammonia), gas having a mass-to-charge ratio m/z of 18 (water), and gashaving a mass-to-charge ratio m/z of 28 (nitrogen molecule) releasedfrom Samples A1 to A3 are shown in FIGS. 48A, 48B, and 48C,respectively.

In FIGS. 47A to 47C and FIGS. 48A to 48C, the lateral axis indicates thetemperature of the samples; here, the temperature range is from 50° C.to 650° C. inclusive. The upper limit temperature of an analysisapparatus used in this example is approximately 650° C. The longitudinalaxis indicates intensity proportional to the amount of each of thereleased gases. The total number of the molecules released to theoutside corresponds to the integral value of the peak. Thus, with thedegree of the peak intensity, the total number of the moleculescontained in the oxide insulating film can be evaluated.

In FIGS. 47A to 47C and FIGS. 48A to 48C, the bold solid line, the thinsolid line, and the dashed line indicate the measurement results ofSamples A1, A2, and A3, respectively.

FIGS. 47A to 47C show that Sample A1 has peaks showing a mass-to-chargeratio m/z of 30 and a mass-to-charge ratio m/z of 44. However, in SampleA1, the peak observed at a temperature range of 150° C. to 200° C. inFIG. 47A is probably due to release of gas other than nitrogen monoxide,and the peak in FIG. 47B is probably due to release of gas other thandinitrogen monoxide. This indicates that release of nitrogen monoxide,dinitrogen monoxide, and nitrogen dioxide are not observed in Sample A1.Sample A2 has peaks showing a mass-to-charge ratio m/z of 30, amass-to-charge ratio m/z of 44, and a mass-to-charge ratio m/z of 46,which shows release of nitrogen monoxide, dinitrogen monoxide, andnitrogen dioxide in Sample A2. Sample A3 does not have peaks showing amass-to-charge ratio m/z of 30, a mass-to-charge ratio m/z of 44, and amass-to-charge ratio m/z of 46. This means that release of nitrogenmonoxide, dinitrogen monoxide, and nitrogen dioxide is not observed inSample A3.

FIG. 48A shows that Sample A1 has a peak showing a mass-to-charge ratiom/z of 17, Sample A2 has lower peak intensity than Sample A1, and SampleA3 has no peak. This indicates that the oxide insulating film includedin Sample A1 contains much ammonia. FIG. 48B shows that Samples A1 andA2 have a peak showing a mass-to-charge ratio m/z of 18. This indicatesthat the oxide insulating films included in Samples A1 and A2 containwater. FIG. 48C shows that Sample A2 has a peak showing a mass-to-chargeratio m/z of 28. This indicates that the oxide insulating film includedin Sample A2 contains nitrogen molecules.

FIG. 49A shows the amounts of gas having a mass-to-charge ratio m/z of30 (nitrogen monoxide), gas having a mass-to-charge ratio m/z of 44(dinitrogen monoxide), gas having a mass-to-charge ratio m/z of 46(nitrogen dioxide), and gas having a mass-to-charge ratio m/z of 28(nitrogen), which were released from Samples A1 and A2, and FIG. 49Bshows the amount of gas having a mass-to-charge ratio m/z of 17 releasedfrom Samples A1 and A2. The amounts of gas were calculated fromintegrated values of the peaks of the curves in FIGS. 47A to 47C andFIGS. 48A to 48C. Note that since the amount of gas having amass-to-charge ratio m/z of 17 released from Sample A2 shows the amountof water adsorbed on a surface of the sample, release of ammonia is notobserved.

As shown in FIG. 49A, the amorous of nitrogen monoxide, dinitrogenmonoxide, nitrogen dioxide, and nitrogen released from Sample A1 aresmaller than those from Sample A2 and are each lower than or equal tothe detection that is, the release of each gas is not detected. Notethat here, the detection limits of nitrogen monoxide, dinitrogenmonoxide, nitrogen dioxide, and nitrogen are 4×10¹⁶ molecules/cm³,4×10¹⁷ molecules/cm³, 4×10¹⁶ molecules/cm³, and 9×10¹⁷ molecules/cm³,respectively. As shown in FIG. 49B, the amount of ammonia released fromSample A2 is larger than that from Sample A1.

FIG. 50 shows the total amounts of nitrogen monoxide, nitrogen dioxide,nitrogen, and ammonia released from Samples A1 and A2.

Table 12 shows the amounts of ammonia, nitrogen, nitrogen monoxide,oxygen, and nitrogen dioxide released from Samples A1 and A2.

TABLE 12 Sample A1 Sample A2 SiH₄ = 50 sccm   SiH₄ = 30 sccm   ReleasedN₂O = 2000 sccm N₂O = 4000 sccm amount 20 Pa, 100 W, 40 Pa, 150 W,[atoms/cm³] 220° C. 220° C. m/z = 17     3.7E19 3.88E+18 (NH₃ or H₂O)(NH₃) (H₂O) m/z = 28 (N₂)  Lower limit or lower 6.80E+18 m/z = 30 (NO)Lower limit or lower 2.80E+18 m/z = 32 (O₂)  Lower limit or lower1.37E+17  m/z = 44 (NO₂) Lower limit or lower 9.90E+16

FIG. 50 shows that the amount of ammonia released from Sample A1 islarger than the total released amount of nitrogen, nitrogen monoxide,and nitrogen dioxide, and the amount of ammonia released from Sample A2is smaller than the total released amount of nitrogen, nitrogenmonoxide, and nitrogen dioxide.

The above results show that, when the flow ratio of dinitrogen monoxideto silane in a source gas is small, an oxide insulating film from whichsmall amounts of nitrogen monoxide, dinitrogen monoxide, nitrogendioxide, and nitrogen are reduced can be formed. The results also showthat an oxide insulating film where the amount of ammonia released islarger than the amount of nitrogen oxide released can be formed.

EXAMPLE 2

The amounts of hydrogen, carbon, nitrogen, and fluorine contained in theoxide insulating films of Samples A1 and A2 fabricated in Example 1 weremeasured by SIMS, and the results are described in this example.

In this example, silicon wafers were used as substrates of Samples A1and A2.

<SIMS Analysis>

SIMS analysis was performed on Samples A1 and A2. The concentration ofeach of hydrogen, carbon, nitrogen, and fluorine in each sample wasmeasured, from the surface of the oxide insulating film (SiON) towardthe silicon wafer (Si). FIGS. 51A and 51B show the measurement resultsof Samples A1 and A2, respectively.

In FIGS. 51A and 51B, the lateral axis indicates a distance from thesurface of the oxide insulating film in the film thickness direction,and the longitudinal axis indicates the concentration of each element.Furthermore, in FIGS. 51A and 51B, the dashed line, the thin solid line,the bold solid line, and the dot-dashed line indicate the concentrationsof hydrogen, carbon, nitrogen, and fluorine, respectively. Note that Siand SiON indicate areas of the silicon water and the oxide insulatingfilm, respectively.

In the oxide insulating film of Sample A1, the hydrogen concentration ishigher than or equal to 2×10²¹ atoms/cm³ and lower than or equal to5×10²¹ atoms/cm³, the nitrogen concentration is higher than or equal to6×10²⁰ atoms/cm³ and lower than or equal to 3×10²¹ atoms/cm³; the carbonconcentration gradually decreases from the surface toward the siliconwafer, and is higher than or equal to 4×10¹⁷ atoms/cm³ and lower than orequal to 5×10²⁰ atoms/cm³; and the fluorine concentration is higher thanor equal to 6×10¹⁸ atoms/cm³ and lower than or equal to 9×10¹⁸atoms/cm³.

In the oxide insulating film of Sample A2, the hydrogen concentration ishigher than or equal to 1×10²¹ atoms/cm³ and lower than or equal to3×10²¹ atoms/cm³; the nitrogen concentration is higher than or equal to1×10²⁰ atoms/cm³ and lower than or equal to 4×10²⁰ atoms/cm³; the carbonconcentration gradually decreases from the surface toward the siliconwafer, and is lower than or equal to the detection limit and lower thanor equal to 6×10¹⁹ atoms/cm³; and the fluorine concentration is higherthan or equal to 7×10¹⁸ atoms/cm³ and lower than or equal to 2×10¹⁸atoms/cm³.

As shown in FIGS. 51A and 51B, the nitrogen concentration in Sample A1is higher than that in Sample A2. This is probably because the oxideinsulating film of Sample A1 contains much NH and NH₃ that do not becomecarrier traps. When the oxide insulating film contains NH, NH₃, and thelike, nitrogen oxide reacts with NH, NH₃, and the like by heattreatment; thus, the content of nitrogen oxide in the oxide insulatingfilm can be reduced.

In the case where the nitrogen concentration of the oxide insulatingfilm is higher than or equal to 6×10²⁰ atoms/cm³, the spin density islower than 1×10¹⁸ spins/cm³, and the oxide insulating film has a reducednumber of defects caused by NO_(x).

EXAMPLE 3

In this example, evaluation results of an oxide insulating film that canbe used for the transistor of one embodiment of the present inventionare described. Specifically, results of evaluating, by IDS analysis, theamounts of ammonia, water, nitrogen, oxygen, and dinitrogen monoxidereleased by heating are described. Note that in this example, unlike inExample 1, TDS analysis was performed on the stack including the oxideinsulating film 23 and the oxide insulating film 25 containing oxygen ata higher proportion than oxygen in the stoichiometric composition, whichis illustrated in FIG. 4A in Embodiment 1.

<Fabrication Methods of Samples>

In this example, Sample A4 that is one embodiment of the presentinvention, and Sample A5 for comparison were fabricated.

<Sample A4>

A 35-nm-thick oxide semiconductor film was formed over a quartzsubstrate by a sputtering method. The oxide semiconductor film wasformed under the following conditions: a sputtering target containingIn, Ga, and Zn at an atomic ratio of 1:1:1 was used; oxygen at a flowproportion of 50% was supplied as a sputtering gas into a treatmentchamber of a sputtering apparatus; the pressure in the treatment chamberwas controlled to 0.6 Pa; and direct-current power of 2.5 kW wassupplied. Note that the oxide semiconductor film was formed at asubstrate temperature of 170° C.

Next, heat treatment was performed at 450° C. in a nitrogen atmospherefor one hour, and after that, another heat treatment was performed at450° C. in a mixed gas of nitrogen and oxygen for one hour.

Subsequently, a first oxide insulating film was formed over the oxidesemiconductor film under the conditions of the oxide insulating film 23described in Embodiment 1, and then, a second oxide insulating film wasformed over the first oxide insulating film under the conditions of theoxide insulating film 25 described in Embodiment 1.

The first oxide insulating film was formed to a thickness of 50 nm by aplasma CVD method under the following conditions: silane with a flowrate of 50 sccm and dinitrogen monoxide with a flow rate of 2000 sccmwere used as a source gas; the pressure in the treatment chamber was 20Pa; the substrate temperature was 220° C.; and a high-frequency power of100 W was supplied to parallel-plate electrodes.

The second oxide insulating film was formed to a thickness of 400 nm bya plasma CVD method under the following conditions: silane at a flowrate of 160 sccm and dinitrogen monoxide at a flow rate of 4000 sccmwere used as a source gas, the pressure in the treatment chamber was 200Pa, the substrate temperature was 220° C., and a high-frequency power of1500 W was supplied to parallel-plate electrodes. Under the aboveconditions, it is possible to form a silicon oxynitride film containingoxygen at a higher proportion than oxygen in the stoichiometriccomposition and from which part of oxygen is released by heating.

Through the above process, Sample A4 of this example was fabricated.

<Sample A5>

Sample A5 was fabricated in a manner similar to that of Sample A4 exceptthat a first oxide insulating film was formed under the followingconditions.

The first oxide insulating film was formed to a thickness of 50 nm by aplasma CVD method under the following conditions: silane with a flowrate of 30 sccm and dinitrogen monoxide with a flow rate of 4000 sccmwere used as a source gas; the pressure in the treatment chamber was 40Pa; the substrate temperature was 220° C.; and a high-frequency power of150 W was supplied to parallel-plate electrodes.

<TDS Analysis>

Thermal desorption spectroscopy (TDS) analyses were performed on SamplesA4 and A5. The amounts of gas having a mass-to-charge ratio m/z of 17(ammonia), gas having a mass-to-charge ratio m/z of 18 (water), and gashaving a mass-to-charge ratio m/z of 28 (nitrogen molecule) releasedfrom Samples A4 and A5 are shown in FIGS. 52A, 52B, and 52C,respectively. In addition, the amounts of gas having a mass-to-chargeratio m/z of 30 (nitrogen monoxide), gas having a mass-to-charge ratiom/z of 32 (oxygen), and gas having a mass-to-charge ratio m/z of 46(nitrogen dioxide) released from Samples A4 and A5 are shown in FIGS.53A, 53B, and 53C, respectively.

In FIGS. 52A to 52C and FIGS. 53A to 53C, the lateral axis indicatesheating temperature; here, the temperature is higher than or equal to50° C. and lower than or equal to 550° C. The longitudinal axisindicates intensity proportional to the amounts of released gases withrespective molecular weights.

In each of FIGS. 52A to 52C and FIGS. 53A to 53C, bold solid line andthe thin solid line indicate the measurement result of Sample A4 andthat of Sample A5, respectively.

FIGS. 52A to 52C show that Samples A4 and A5 have peaks showing amass-to-charge ratio m/z of 17, a mass-to-charge ratio m/z of 18, and amass-to-charge ratio m/z of 28. The intensities of the peaks showing amass-to-charge ratio m/z of 17, a mass-to-charge ratio m/z of 18, and amass-to-charge ratio m/z of 28 of Sample A4 are higher than those ofSample A5. This means that Sample A4 releases larger amounts of ammonia,water, and nitrogen molecules than Sample A5.

Since Samples A4 and A5 each include the second oxide insulating filmcontaining oxygen at a higher proportion than oxygen in thestoichiometric composition, it is probable that nitrogen oxide containedin the first oxide insulating film reacts with oxygen by heat treatment,so that water and nitrogen are released.

FIGS. 53A to 53C show that Sample A5 has peaks showing a mass-to-chargeratio m/z of 30, a mass-to-charge ratio m/z of 32, and a mass-to-chargeratio m/z of 46. The intensities of the peaks showing a mass-to-chargeratio m/z of 30, a mass-to-charge ratio m/z of 32, and a mass-to-chargeratio m/z of 46 of Sample A4 are lower than those of Sample A5. Thismeans that Sample A4 releases smaller amounts of nitrogen monoxide,oxygen, and nitrogen dioxide than Sample A5. In addition, Sample A4releases small amounts of nitrogen monoxide, oxygen, and nitrogendioxide at a temperature higher than or equal to 300° C.

FIGS. 52A to 52C and FIGS. 53A to 53C show that Sample A4 releaseslarger amounts of water and nitrogen and smaller amounts of nitrogenmonoxide, oxygen, and nitrogen dioxide than Sample A5. Accordingly, theamount of nitrogen oxide which is contained in the first oxideinsulating film, reacts with ammonia, and is released as nitrogenmolecules and water is probably larger in Sample A4 than in Sample A5.In other words, the reactions represented by Reaction Formulae (A-1) and(A-2) described in Embodiment 1 probably occur.

EXAMPLE 4

The amounts of hydrogen, carbon, nitrogen, and fluorine contained inoxide insulating films were measured by SIMS, and the results aredescribed in this example.

<Fabrication Methods of Samples>

In this example, Sample A6 that is one embodiment of the presentinvention, and Sample A7 for comparison were fabricated.

<Sample A6>

First, over a glass substrate, a silicon nitride film with a thicknessof 400 nm was formed and then, a silicon oxynitride film with athickness of 50 nm was formed. Then, an oxide semiconductor film (“IGZO”in FIGS. 54A and 54B and FIGS. 55A and 55B) with a thickness of 35 nmwas formed over the silicon oxynitride film by a sputtering method. Theoxide semiconductor film was formed under the deposition conditions ofthe oxide semiconductor film in Sample A4 described in Example 3.

Next, heat treatment was performed at 450° C. in a nitrogen atmospherefor one hour, and after that, another heat treatment was performed at450° C. in a mixed gas of nitrogen and oxygen for one hour.

After that, a first oxide insulating film (“1st SiON” in FIGS. 54A and54B and FIGS. 55A and 55B) with a thickness of 50 nm was formed over theoxide semiconductor film under the conditions of the oxide insulatingfilm 23 described in Embodiment 1. Then, a second oxide insulating film(“2nd SiON” in FIGS. 54A and 54B and FIGS. 55A and 55B) with a thicknessof 400 nm was formed over the first oxide insulating film under theconditions of the oxide insulating film 25 described in Embodiment 1.

The first oxide insulating film was formed under the depositionconditions of the first oxide insulating film in Sample A4 described inExample 3.

The second oxide insulating film was formed under the depositionconditions of the second oxide insulating film in Sample A4 described inExample 3.

Next, heat treatment was performed at 350° C. in an atmosphere ofnitrogen and oxygen for one hour and after that, a silicon nitride filmwith a thickness of 100 nm was formed.

Through the above process, Sample A6 of this example was fabricated.

<Sample A7>

Sample A7 was fabricated in a manner similar to that of Sample A6 exceptthat the first oxide insulating film was formed under the depositionconditions of the first oxide insulating film in Sample A5 described inExample 3.

<SIMS Analysis>

SIMS analysis was performed on Samples A6 and A7. Note that in eachsample, the concentrations of hydrogen, carbon, nitrogen, and fluorinewere measured from a surface of the second oxide insulating film (2ndSiON) to the oxide semiconductor film (IGZO). FIGS. 54A and 54B showmeasurement results of the hydrogen concentration and the secondary ionintensity of silicon in Sample A6 and Sample A7, respectively. FIGS. 55Aand 55B show measurement results of concentrations of carbon, nitrogen,and fluorine in Sample A6 and Sample A7, respectively.

In each of FIGS. 54A and 54B and FIGS. 55A and 55B, the lateral axisindicates a distance in the thickness direction and the leftlongitudinal axis indicates the concentration of each element. In eachof FIGS. 54A and 54B, the right longitudinal axis indicates thesecondary ion intensity of silicon. In addition, in each of FIGS. 54Aand 54B, a dashed line indicates the concentration of hydrogen and adashed double-dotted line indicates the secondary ion intensity ofsilicon. In each of FIGS. 55A and 55B, a thin solid line, a thick solidline, and a dashed-dotted line indicate the concentration of carbon, theconcentration of nitrogen, and the concentration of fluorine,respectively.

FIG. 54A shows that the hydrogen concentration in Sample A6 is almostthe same in the first oxide insulating film (1st SiON) and the secondoxide insulating film (2nd SiON), and is greater than or equal to 1×10²¹atoms/cm³ and less than or equal to 2×10²¹ atoms/cm³, specifically.

FIG. 55A shows that the nitrogen concentration in the first oxideinsulating film (1st SiON) is higher than that in the second oxideinsulating film (2nd SiON). Specifically, the nitrogen concentration inthe first oxide insulating film (1st SiON) is greater than or equal to3×10¹¹ atoms/cm³ and less than or equal to 6×10²¹ atoms/cm³, and thenitrogen concentration in the second oxide insulating film (2nd SiON) isgreater than or equal to 9×10²⁰ atoms/cm³ and less than or equal to1×10²¹ atoms/cm³.

The carbon concentration is almost the same in the first oxideinsulating film (1st SiON) and the second oxide insulating film (2ndSiON); however, the carbon concentration slightly increases at theinterface between the first oxide insulating film (1st SiON) and theoxide semiconductor film (IGZO). Specifically, the carbon concentrationin the first oxide insulating film (1st SiON) and the second oxideinsulating film (2nd SiON) is greater than or equal to 1×10¹⁷ atoms/cm³and less than or equal to 7×10¹⁷ atoms/cm³.

Furthermore, the fluorine concentration is almost the same in the firstoxide insulating film (1st SiON) and the second oxide insulating film(2nd SiON); however, the fluorine concentration slightly increases atthe interface between the second oxide insulating film (2nd SiON) andthe first oxide insulating film (1st SiON) and at the interface betweenthe first oxide insulating film (1st SiON) and the oxide semiconductorfilm (IGZO), and has a peak. Specifically, the fluorine concentration inthe first oxide insulating film (1st SiON) and the second oxideinsulating film (2nd SiON) is greater than or equal to 1×10¹⁹ atoms/cm³and less than or equal to 1×10²⁰ atoms/cm³.

FIG. 54B shows that, as in the case of Sample A6, the hydrogenconcentration in Sample A7 is almost the same in the first oxideinsulating film (1st SiON) and the second oxide insulating film (2ndSiON), and is greater than or equal to 8×10²⁰ atoms/cm³ and less than orequal to 2×10²¹ atoms/cm³, specifically.

FIG. 55B shows that, unlike in Sample A6, the nitrogen concentration isalmost the same in the first oxide insulating film (1st SiON) and thesecond oxide insulating film (2nd SiON), and is greater than or equal to8×10¹⁹ atoms/cm³ and less than or equal to 2×10²⁰ axioms/cm³,specifically.

As in the case of Sample A6, the carbon concentration is almost the samein the first oxide insulating film (1st SiON) and the second oxideinsulating film (2nd SiON); however, the carbon concentration slightlyincreases at the interface between the first oxide insulating film (1stSiON) and the oxide semiconductor film (IGZO). Specifically, the carbonconcentration in the first oxide insulating film (1st SiON) and thesecond oxide insulating film (2nd SiON) is greater than or equal to6×10¹⁶ atoms/cm³ and less than or equal to 7×10¹⁷ atoms/cm³.

Furthermore, as in the case of Sample A6, the fluorine concentration isalmost the same in the first oxide insulating film (1st SiON) and thesecond oxide insulating film (2nd SiON); however, the fluorineconcentration slightly increases at the interface between the secondoxide insulating film (2nd SiON) and the first oxide insulating film(1st SiON) and at the interface between the first oxide insulating film(1st SiON) and the oxide semiconductor film (IGZO), and has a peak.Specifically, the fluorine concentration in the first oxide insulatingfilm (1st SiON) and the second oxide insulating film (2nd SiON) isgreater than or equal to 1×10¹⁹ atoms/cm³ and less than or equal to8×10¹⁹ atoms/cm³.

Note that in Samples A6 and A7, peaks are observed at the interfacebetween the second oxide insulating film (2nd SiON) and the first oxideinsulating film (1st SiON) and the interface between the first oxideinsulating film (1st SiON) and the oxide semiconductor film (IGZO). Thisis because of the following reason. After the oxide semiconductor film(IGZO) was formed in a first treatment chamber, the sample wastransferred to a second treatment chamber. Next, after the flow rate ofa source gas introduced into the second treatment chamber and thepressure in the second treatment chamber were adjusted, a plasma CVDapparatus was powered on to form the first oxide insulating film (1stSiON). After the plasma CND apparatus was powered off once, the flowrate of a source gas introduced into the second treatment chamber andthe pressure in the treatment chamber were changed. Then, the plasma CVDapparatus was powered on again to form the second oxide insulating film(2nd SiON). This means that a surface of the sample was exposed to anatmosphere in the treatment chamber until formation of each of the firstoxide insulating film (1st SiON) and the second oxide insulating film(2nd SiON) started.

On inner walls of the treatment chambers, fluorine or NF₃ that was usedin cleaning of the treatment chambers was attached. For this reason,fluorine or NF₃ was detached from the inner walls of the treatmentchambers and attached to a surface of each sample before formation ofeach of the first oxide insulating film (1st SiON) and the second oxideinsulating film (2nd SiON) started. As a result, the fluorineconcentration is high at the interface between the second oxideinsulating film (2nd SiON) and the first oxide insulating film (1stSiON) and the interface between the first oxide insulating film (1stSiON) and the oxide semiconductor film (IGZO) and has a peak.

From the above, a state of stacking of oxide insulating films can beexamined by measuring an impurity concentration in the oxide insulatingfilms over the oxide semiconductor film by SIMS.

As shown in FIGS. 55A and 55B, the nitrogen concentration in Sample A6is higher than that in Sample A7. This is probably because the oxideinsulating film of Sample A6 contains much NH and NH₃ that do not becomecarrier traps. When the oxide insulating film contains NH, NH₃, and thelike, nitrogen oxide reacts with NH, NH₃, and the like by heattreatment; thus, the content of nitrogen oxide in the oxide insulatingfilm can be reduced.

EXAMPLE 5

In this example, the number of defects in the oxide insulating film isdescribed using the measurement results of ESR.

<Fabrication Methods of Samples 1>

Fabrication methods of Samples B1 to B3 of this example are describedbelow.

<Sample B1>

First, a first oxide insulating film and a second oxide insulating filmwere formed under conditions similar to those of Sample A4 described inExample 3.

Next, by heat treatment, water, nitrogen, hydrogen, and the like werereleased from the first oxide insulating film and the second oxideinsulating film and part of oxygen contained in the second oxideinsulating film was supplied to the oxide semiconductor film. Here, theheat treatment was performed at 350° C. in a mixed atmosphere ofnitrogen and oxygen for one hour.

Through the above process, Sample B1 of this example was fabricated.

<Sample B2>

Sample B2, which was used for comparison, was fabricated under the sameconditions as those of Sample B1 except for the formation pressure ofthe first oxide insulating film. Specifically, a sample including afirst oxide insulating film formed under the following conditions wasfabricated as Sample B2.

In Sample B2, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane with a flow rate of 50sccm and dinitrogen monoxide with a flow rate of 2000 sccm were used asa source gas; the pressure in the treatment chamber was 100 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes.

<Sample B3>

Sample B3, which was used for comparison, was fabricated under the sameconditions as those of Sample B1 except for the formation pressure ofthe first oxide insulating film. Specifically, a sample including afirst oxide insulating film formed under the following conditions wasfabricated as Sample B3.

In Sample B3, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 50 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 200 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes.

<ESR Measurement>

Next, Samples B1 to B3 were measured by ESR measurement. Here, the ESRmeasurement was performed under the following conditions. Themeasurement temperature was −170° C., the high-frequency power (power ofmicrowaves) of 8.92 GHz was 1 mW, and the direction of a magnetic fieldwas parallel to a surface of each sample. The detection limit of thespin density of a signal attributed to NO_(x) is 4.7×10¹⁵ spins/cm³.This means that when the number of spins is small, the number of defectsis small in the film.

The spin densities of the signals attributed to NO_(x) of Samples B1 toB3 are shown in FIGS. 56A to 56C, respectively. Note that shown here isthe spin densities obtained by converting the number of measured spinsinto that per unit volume.

As shown in FIGS. 56A to 56C, in Samples B1 to B3, a first signal thatappears at a g-factor of greater than or equal to 2.037 and less than orequal to 2.039, a second signal that appears at a g-factor of greaterthan or equal to 2.001 and less than or equal to 2.003, and a thirdsignal that appears at a g-factor of greater than or equal to 1.964 andless than or equal to 1.966 are observed. These three signals are due toNO_(x) and represent splits of a hyperfine structure arising from thenuclear spin of an N atom. The signals attributed to NO_(x) haveanisotropic spin species and thus the waveform is asymmetrical.

The spin density of the signals attributed to NO_(x) in Samples B2 andB3 is higher than that in Sample B1, and thus the oxide insulating filmsof Samples B2 and B3 have a large number of detects. In FIGS. 56A to56C, the spin density of the signals attributed to NO_(x) in Sample B1is the smallest. Thus, it is shown that when the first oxide insulatingfilm to be in contact with the oxide semiconductor film is formed inhigh vacuum, the oxide insulating film having a reduced number ofdefects is formed.

<Fabrication Methods of Samples 2>

Next, Samples B4 and B5 were fabricated: the formation pressure of thefirst oxide insulating film was fixed at the pressure of Sample B1 whichobtained excellent results in the ESR measurement, and the flow ratio ofthe deposition gas was changed. The number of defects of Samples B4 andB5 were measured. The fabrication methods of Samples B4 and B5 are shownbelow.

<Sample B4>

Sample B4, which was used for comparison, was fabricated under the sameconditions as those of Sample B1 except for the flow ratio of thedeposition gas for the first oxide insulating film. Specifically, asample including a first oxide insulating film formed under thefollowing conditions was fabricated as Sample B4.

In Sample B4, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 20 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 100 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes. In other words, when the flowratio of silane was 1, the flow ratio of dinitrogen monoxide was 100.

<Sample B5>

Sample B5, which was used for comparison, was fabricated under the sameconditions as those of Sample B1 except for the flow ratio of thedeposition gas for the first oxide insulating film. Specifically, asample including a first oxide insulating film formed under thefollowing conditions was fabricated as Sample B5.

In Sample B5, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 100 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 200 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes. In other words, when the flowrate of silane was 1, the flow rate of dinitrogen monoxide was 20.

<ESR Measurement>

Samples B1, B4, and B5 were measured by ESR measurement. FIGS. 57A, 57B,and 57C show the ESR measurement results of Samples B4, B1, and B5,respectively. The conditions of the ESR measurement were similar tothose for FIGS. 56A to 56C.

As shown in FIGS. 57A and 57B, the spin densities of signals attributedto NO_(x) are higher in Sample B4, which was used for comparison, thanin Sample B1, and thus oxide insulating film of Samples B4 has a largenumber of defects. As shown in FIG. 57C, in Sample B5, which was usedfor comparison, the spin densities of signals attributed to NO_(x) arelower than or equal to the detection limit, and a signal attributed toV_(O)H that appears at a g (g-factor) of 1.93 is observed.

EXAMPLE 6

In this example, examination results of the V_(g)-I_(d) characteristicsand the reliability of fabricated transistors are described.

<Fabrication Methods of Samples 1>

As Samples C1 to C3 of this example, transistors having the samestructure as that of the transistor 10 a in FIG. 4A described inEmbodiment 1 were fabricated.

<Sample C1>

First, a glass substrate was used as the substrate 11, and the gateelectrode 13 was formed over the substrate 11.

The gate electrode 13 was formed in the following manner: a 100-nm-thicktungsten film was formed by a sputtering method, a mask was formed overthe tungsten film by a photolithography process, and the tungsten filmwas partly etched using the mask.

Next, the gate insulating film 15 was formed over the gate electrode 13.

As the gate insulating film 15, a stack including a 400-nm-thick siliconnitride film and a 50-nm-thick silicon oxynitride film was used.

Note that the silicon nitride film was formed to have a three-layerstructure of a first silicon nitride film, a second silicon nitridefilm, and a third silicon nitride film.

The first silicon nitride film was formed to a thickness of 50 nm underthe following conditions: silane at a flow rate of 200 sccm, nitrogen ata flow rate of 2000 sccm, and an ammonia gas at a flow rate of 100 sccmwere supplied to a treatment chamber of a plasma CVD apparatus as asource gas; the pressure in the treatment chamber was controlled to 100Pa; and power of 2000 W was supplied with the use of a 27.12 MHzhigh-frequency power source.

The second silicon nitride film was formed to a thickness of 300 nmunder the following conditions: silane at a flow rate of 200 sccm,nitrogen at a flow rate of 2000 sccm, and an ammonia gas at a flow rateof 2000 sccm were supplied to the treatment chamber of the plasma CVDapparatus as a source gas; the pressure in the treatment chamber wascontrolled to 100 Pa; and power of 2000 W was supplied with the use of a27.12 MHz high-frequency power source.

The third silicon nitride film was formed to a thickness of 50 nm underthe following conditions: silane at a flow rate of 200 sccm and nitrogenat a flow rate of 5000 sccm were supplied to the treatment chamber ofthe plasma CVD apparatus as a source gas; the pressure in the treatmentchamber was controlled to 100 Pa; and power of 2000 W was supplied withthe use of a 27.12 MHz high-frequency power source. Note that the firstsilicon nitride film, the second silicon nitride film, and the thirdsilicon nitride film were each formed at a substrate temperature of 350°C.

The silicon oxynitride film was formed under the following conditions:silane at a flow rate of 20 sccm and dinitrogen monoxide at a flow rateof 3000 sccm were supplied to the treatment chamber of the plasma CVDapparatus as a source gas; the pressure in the treatment chamber wascontrolled to 40 Pa; and power of 100 W was supplied with the use of a27.12 MHz high-frequency power source. Note that the silicon oxynitridefilm was formed at a substrate temperature of 350° C.

Next, the oxide semiconductor film 17 was formed to overlap with thegate electrode 13 with the gate insulating film 15 positionedtherebetween.

Here, a 35-nm-thick oxide semiconductor film was formed over the gateinsulating film 15 by a sputtering method, a mask was formed over theoxide semiconductor film by a photolithography process, and part of theoxide semiconductor film was etched with the use of the mask, wherebythe oxide semiconductor film 17 (S2-IGZO in FIG. 58) was formed.

The oxide semiconductor film 17 was formed under the followingconditions: an In—Ga—Zn oxide sputtering target containing In, Ga, andZn at an atomic ratio of 1:1:1 was used; oxygen at a flow proportion of50% was supplied as a sputtering gas into a treatment chamber of asputtering apparatus; the pressure in the treatment chamber wascontrolled to 0.6 Pa; and direct-current power of 2.5 kW was supplied.Note that the oxide semiconductor film was formed at a substratetemperature of 170° C.

Next, heat treatment was performed at 450° C. in a nitrogen atmospherefor one hour, and after that, another heat treatment was performed in amixed gas of nitrogen and oxygen at 450° C. for one hour.

Next, the pair of electrodes 19 and 20 in contact with the oxidesemiconductor film 17 were formed.

First, a conductive film was formed over the gate insulating film andthe oxide semiconductor film. As the conductive film, a 400-nm-thickaluminum film was formed over a 50-nm-thick tungsten film, and a100-nm-thick titanium film was formed over the aluminum film. Then, amask was formed over the conductive film by a photolithography process,and the conductive film was partly etched using the mask. Through theabove steps, the pair of electrodes 19 and 20 were formed.

Next, the substrate was transferred to a treatment chamber in a reducedpressure and heated at 220° C. Then, the oxide semiconductor film 17 wasexposed to oxygen plasma that was generated in a dinitrogen monoxideatmosphere by supply of a high-frequency power of 150 W to an upperelectrode in the treatment chamber with the use of a 27.12 MHzhigh-frequency power source.

After that, the protective film 21 was formed over the oxidesemiconductor film 17 and the pair of electrodes 19 and 20. In thiscase, the protective film 21 was formed to have a three-layer structureof a first oxide insulating film (P1-SiON in FIG. 58), a second oxideinsulating film (P2-SiON in FIG. 58), and a nitride insulating film.

The 50-nm-thick first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 50 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 20 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes.

The formation conditions of the first oxide insulating film of Sample C1is the same as those of the first oxide insulating film of Sample A4described in Example 3.

The 400-nm-thick second oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 160 sccmand dinitrogen monoxide at a flow rate of 4000 sccm were used as asource gas, the pressure in the treatment chamber was 200 Pa, thesubstrate temperature was 220° C., and a high-frequency power of 1500 Wwas supplied to parallel-plate electrodes. Under the above conditions,it is possible to form a silicon oxynitride film that contains oxygen ata higher proportion than oxygen in the stoichiometric composition sothat part of oxygen is released by heating.

Next, heat treatment was performed to release water, nitrogen, hydrogen,and the like from the first oxide insulating film and the second oxideinsulating film and to supply part of oxygen contained in the secondoxide insulating film into the oxide semiconductor film. Here, the heattreatment was performed at 350° C. in a mixed atmosphere of nitrogen andoxygen for one hour.

Then, a 100-nm-thick nitride insulating film was formed over the secondoxide insulating film. The nitride insulating film was formed by aplasma CVD method under the following conditions: silane at a flow rateof 50 sccm, nitrogen at a flow rate of 5000 sccm, and an ammonia gas ata flow rate of 100 sccm were used as a source gas; the pressure in thetreatment chamber was 100 Pa; the substrate temperature was 350° C.; anda high-frequency power of 1000 W was supplied to parallel-plateelectrodes.

Next, a planarization film was formed (not illustrated) over theprotective film Here, the protective film 21 was coated with acomposition, and exposure and development were performed, so that aplanarization film having an opening through which the pair ofelectrodes are partly exposed was formed. Note that as the planarizationfilm, a 1.5-μm-thick acrylic resin was formed. Then, heat treatment wasperformed. The heat treatment was performed in a nitrogen atmosphere at250° C. for one hour.

Then, an opening was formed in part of the protective film 21 so thatthe opening reached one of the pair of electrodes 19 and 20. The openingportion was formed in the following manner: a mask was formed over theprotective film 21, and the protective film 21 was partly etched usingthe mask.

Next, a pixel electrode was formed over the planarization film so thatthe pixel electrode was electrically connected to one of the pair ofelectrodes 19 and 20 through the opening formed in parts of theprotective film 21 and the planarization film.

Here, as the pixel electrode, a conductive film of an indium oxide-tinoxide compound (ITO-SiO₂) containing silicon oxide was formed by asputtering method. Note that the composition of a target used forforming the conductive film was In₂O₃:SnO₂:SiO₂=85:10:5 [wt %]. Afterthat, heat treatment was performed at 250° C. in a nitrogen atmospherefor one hour.

Through the above process, Sample C1 of this example was fabricated.

<Sample C2>

Sample C2 was fabricated under the same conditions as those of Sample C1except for the formation pressure of the first oxide insulating film.Specifically, a sample including a first oxide insulating film formedunder the following conditions was fabricated as Sample C2.

In Sample C2, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 50 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 100 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes.

The formation conditions of the first oxide insulating film of Sample C2is the same as those of the first oxide insulating film of Sample B2described in Example 5.

<Sample C3>

Sample C3, which was used for comparison, was fabricated under the sameconditions as those of Sample C1 except for the formation pressure ofthe first oxide insulating film. Specifically, a sample including afirst oxide insulating film formed under the following conditions wasfabricated as Sample C3.

In Sample C3, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane with a flow rate of 50sccm and dinitrogen monoxide with a flow rate of 2000 sccm were used asa source gas; the pressure in the treatment chamber was 200 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes.

The formation conditions of the first oxide insulating film of Sample C3is the same as those of the first oxide insulating film of Sample B3described in Example 5.

<V_(g)-I_(d) Characteristics>

Next, initial V_(g)-I_(d) characteristics of the transistors included inSamples C1 to C3 were measured. Here, changes in characteristics ofcurrent flowing between a source and a drain (hereinafter referred to asdrain current: I_(d)), that is, V_(g)-I_(d) characteristics weremeasured under the following conditions: the substrate temperature was25° C., the potential difference between the source and the drain(hereinafter referred to as drain voltage: V_(d)) was 1 V or 10 V, andthe potential difference between the source and the gate electrodes(hereinafter referred to as gate voltage: V_(g)) was changed from −15 Vto 15 V.

FIG. 58 shows V_(g)-I_(d) characteristics of Samples C1 to C3. FIG. 58shows the results of transistors each having a channel length L of 6 μmand a channel width W of 50 μm. In FIG. 58, the lateral axis, the firstlongitudinal axis, and the second longitudinal axis represent gatevoltage V_(g), drain current I_(d), and field-effect mobility,respectively. Here, to show field-effect mobility in a saturationregion, field-effect mobility calculated when V_(d)=10 V is shown.

As shown in FIG. 58, Samples C1 and C2 have excellent initialV_(g)-I_(d) characteristics. In contrast, Sample C3, which was used forcomparison and in which the formation pressure of the first oxideinsulating film was 200 Pa, has variations in V_(g)-I_(d)characteristics.

<Gate BT Stress Test>

Next, a gate BT stress test (GBT) and a gate BT photostress test (PGBT)were performed on Samples C1 to C3.

First, a gate BT stress test and a gate BT photostress test wereperformed.

A measurement method of the gate BT stress test is described. First,substrate temperature is kept constant at given temperature(hereinafter, referred to as stress temperature) to measure the initialV_(g)-I_(d) characteristics of the transistor.

Next, while the substrate temperature is kept at stress temperature, thepair of electrodes serving as a source electrode and a drain electrodeof the transistor is set at the same potential and the gate electrode issupplied with a potential different from that of the pair of electrodesfor a certain period of time (hereinafter referred to as stress time).Then, the V_(g)-I_(d) characteristics of the transistor are measuredwhile the substrate temperature is kept at the stress temperature, As aresult, a difference in threshold voltage and a difference in shiftvalue between before and after the gate BT stress test can be obtainedas the amount of change in the electrical characteristics.

Note that a stress test where negative voltage is applied to a gateelectrode is called negative gate BT stress test (dark negative stress)whereas a stress test where positive voltage is applied is calledpositive gate BT stress test (dark positive stress). Note that a stresstest where negative voltage is applied to a gate electrode while lightemission is performed is called negative gate BT photostress test(negative photostress whereas a stress test where positive voltage isapplied while light emission is performed is called positive gate BTphotostress test (positive photostress).

Here, the gate BT stress conditions were as follows: stress temperaturewas 60° C., stress time was 3600 seconds, −30 V or +30 V was applied tothe gate electrode, and 0 V was applied to the pair of electrodesserving as the source electrode and the drain electrode. The electricfield intensity applied to the gate insulating film was 0.66 MV/cm.

Under the same conditions as those of the above gate BT stress test, thegate BT photostress test was performed where the transistor wasirradiated with white light with 10000 1× using an LED. Note that theV_(g)-I_(d) characteristics of the transistor were measured at atemperature of 60° C. after each of the BT stress tests.

FIG. 59 shows a difference between threshold voltage in the initialcharacteristics and threshold voltage after the BT stress test (i.e.,the amount of change in threshold voltage (ΔV_(th))) and a difference inshift value (i.e., the amount of change in the shift value (ΔShift)) ofrespective transistors included in Samples C1 to C3.

Here, a threshold voltage and a shift value in this specification aredescribed. Threshold voltage V_(th) is defined as, in the V_(g)-I_(d)curve where the lateral axis represents gate voltage V_(g) [V] and thelongitudinal axis represents the square root of drain current I_(d)(I_(d) ^(1/2)) [A^(1/2)], gate voltage at the intersection point of theline of I_(d) ^(1/2)=0 (V_(g) axis) and the tangent to the curve at apoint where the slope of the curve is the steepest. Note that here, thethreshold voltage is calculated with a drain voltage V_(d) of 10 V.

Furthermore, shift value Shift in this specification is defined as, inthe V_(g)-I_(d) curve where the lateral axis represents the gate voltageV_(g) [V] and the longitudinal axis represents the logarithm of thedrain current I_(d) [A], gate voltage at the intersection point of theline of I_(d)=1.0×10¹² [A] and the tangent to the curve at a point wherethe slope of the curve is the steepest. Note that here, the shift valueis calculated with a drain voltage V_(d) of 10 V.

From FIG. 59, the amount of change in the threshold voltage and theamount of change in the shift value of Samples C1 and C2 were smallerthan those of Sample C3, which was used for comparison. In particular,in Sample C1, the amount of change in the threshold voltage and theamount of change in the shift value were small in the positive gate BTphotostress test and the negative gate BT photostress test.

<Fabrication Methods of Samples 2>

Next, Samples C4 and C5 were fabricated: the formation pressure of thefirst oxide insulating film was fixed at the pressure of Sample C 1,which obtained the excellent V_(g)-I_(d) characteristics and excellentresults in the gate BT stress test, and the flow ratio of the depositiongas was changed. The V_(g)-I_(d) characteristics and reliability ofSamples C4 and C5 were measured. The fabrication methods of Samples C4and C5 are shown below:

<Sample C4>

Sample C4 was fabricated under the same conditions as those of Sample C1except for the flow ratio of the deposition gas for the first oxideinsulating film. Specifically, a sample including a first oxideinsulating film formed under the following conditions was fabricated asSample C4.

In Sample C4, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 20 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 100 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes. In other words, when the flowrate of silane was 1, the flow rate of dinitrogen monoxide was 100.

The formation conditions of the first oxide insulating film of Sample C4is the same as those of the first oxide insulating film of Sample B4described in Example 5.

<Sample C5>

Sample C5, which was used for comparison, was fabricated under the sameconditions as those of Sample C1 except for the flow ratio of thedeposition gas for the first oxide insulating film. Specifically, asample including a first oxide insulating film formed under thefollowing conditions was fabricated as Sample C5.

In Sample C5, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 100 sccmand dinitrogen monoxide at a flow rate of 2000 sccm were used as asource gas; the pressure in the treatment chamber was 200 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes. In other words, when the flowrate of silane was 1, the flow rate of dinitrogen monoxide was 20.

The formation conditions of the first oxide insulating film of Sample C5is the same as those of the first oxide insulating film of Sample B5described in Example 5.

<V_(g)-I_(d) Characteristics>

Next, initial V_(g)-I_(d) characteristics of the transistors included inSamples C1, C4, and C5 were measured. Here, changes in drain currentI_(d), that is, V_(g)-I_(d) characteristics were measured under thefollowing conditions: the substrate temperature was 25° C. the drainvoltage V_(d) was 1 V or 10 V and the gate voltage V_(g) was changedfrom −15 V to 15 V.

FIG. 60 shows V_(g)-I_(d) characteristics of Samples C1, C4, and C5.FIG. 60 shows the results of transistors having a channel length L of 6μm and a channel width W of 50 μm. In FIG. 60, the lateral axis, thefirst longitudinal axis, and the second longitudinal axis represent gatevoltage V_(g), drain current I_(d), and field-effect mobility,respectively. Here, to show field-effect mobility in a saturationregion, field-effect mobility calculated when V_(d)=10 V is shown.

As shown in FIG. 60, Samples C1 and C4 have excellent initialV_(g)-I_(d) characteristics. In contrast, in Sample C5, which was usedfor comparison, the on-off ratio of the drain current is not obtained;thus, the transistor characteristics are not obtained. In considerationof the results of Sample B5 described in Example 5, this is probablybecause the oxide semiconductor film contains a large number of oxygenvacancies.

<Gate BT Stress Test>

Next, a gate BT stress test and a gate BT photostress test wereperformed on Samples C1, C4, and C5.

Specifically, a positive gate BT stress test (dark positive stress), anegative gate BT stress test (dark negative stress), a positive gate BTphotostress test (positive photostress), and a negative gate BTphotostress test (negative photostress) were performed. FIG. 61 showsthe difference between the initial threshold voltage and the thresholdvoltage after the gate BT stress test (i.e., the amount of change in thethreshold voltage (ΔV_(th))) and the difference between the initialshift value and the shift value after the gate BT stress test (i.e., theamount of change in the shift value (ΔShift)) of transistors of SamplesC1, C4, and C5.

As shown in FIG. 61, the amount of change in the threshold voltage andthe amount of change in the shift value were greater in Sample C4, whichwas used for comparison and in which the flow ratio of dinitrogenmonoxide to silane was 100 in forming the first oxide insulating film,than in Sample C1 of one embodiment of the present invention in whichthe flow ratio of dinitrogen monoxide to silane was 40.

According to Example 5 and this example, the oxide insulating film incontact with the oxide semiconductor film in Sample C1 has a small spindensity, in other words, a small number of defects, and thus the amountof change in the threshold voltage and the amount of change in the shiftvalue of the transistor are small.

<Fabrication Methods of Samples 3>

Next, Samples C6 and C7 were fabricated by changing at least one of theflow ratio of the deposition gas, the pressure, and the formationtemperature. The V_(g)-I_(d) characteristics and reliability of SamplesC6 and C7 were measured. The fabrication methods of Samples C6 and C7are shown below.

<Sample C6>

Sample C6, which was used for comparison, was fabricated under the sameconditions as those of Sample C1 except for the flow ratio of thedeposition gas for the first oxide insulating film. Specifically, asample including a first oxide insulating film formed under thefollowing conditions was fabricated as Sample C6.

In Sample C6, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 30 sccmand dinitrogen monoxide at a flow rate of 4000 sccm were used as asource gas; the pressure in the treatment chamber was 40 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes. In other words, when the flowrate of silane was 1, the flow rate of dinitrogen monoxide was 133.

<Sample C7>

Sample C7, which was used for comparison, was fabricated under the sameconditions as those of Sample C1 except for the flow ratio of thedeposition gas for the first oxide insulating film. Specifically, asample including a first oxide insulating film formed under thefollowing conditions was fabricated as Sample C7.

In Sample C7, the first oxide insulating film was formed by a plasma CVDmethod under the following conditions: silane at a flow rate of 20 sccmand dinitrogen monoxide at a flow rate of 3000 sccm were used as asource gas; the pressure in the treatment chamber was 200 Pa; thesubstrate temperature was 350° C.; and a high-frequency power of 100 Wwas supplied to parallel-plate electrodes. In other words, when the flowrate of silane was 1, the flow rate of dinitrogen monoxide was 150.

<Gate BT Stress Test>

Next, a gate BT stress test and a gate BT photostress test wereperformed on Samples C6 and C7. Here, the description of the testresults is omitted.

A sample having a structure similar to that described in Example 5 wasfabricated using the same conditions as those of the oxide semiconductorfilm, the first oxide insulating film, and the second oxide insulatingfilm of Sample C6. This sample is referred to as Sample B6. A samplehaving a structure described in Example 5 was fabricated using the sameconditions as those the oxide semiconductor film, the first oxideinsulating film, and the second oxide insulating film of Sample C7. Thissample is referred to as Sample B7. ESR measurement was performed alsoin Samples B6 and B7, and the spin density of signals attributed toNO_(x) was obtained. Here, the description of the measurement results ofESR is omitted.

<Amount of Change in Spin Density and Amount of Change in ThresholdVoltage of Oxide Insulating Film>

FIG. 62 shows the spin density of the samples obtained in Example 5 andthe amount of change in the threshold voltage of the samples obtained inExample 6. Here, the lateral axis indicates the spin densities ofSamples B1, B2, B4, B6, and B7, and the longitudinal axis indicates theamount of change in the threshold voltage due to a negative gate BTstress test (dark negative stress) of Samples C1, C2, C4, C6, and C7.

FIG. 62 shows that when the spin density of each sample is small, theamount of change in threshold voltage is small. In Samples B1, B2, B4,B6, B7, C1, C2, C4, C6, and C7, the formation conditions of the oxidesemiconductor film and the second oxide insulating film were the same,and when the spin density of signals attributed to NO_(x) of the firstoxide insulating film is lower than, typically, 1×10¹⁸ spins/cm³, theamount of change in the threshold voltage was small.

EXAMPLE 7

In this example, examination results of the V_(g)-I_(d) characteristicsand the reliability of fabricated transistors are described.

<Fabrication Methods of Samples>

As Sample G1 of this example, a transistor having the same structure asthat of the transistor 10 a in FIG. 4A described in Embodiment 1 wasfabricated. Furthermore, as Samples G2 and G6 of this example,transistors having the same structure as that of the transistor 10 e inFIGS. 6A to 6C described in Embodiment 1 were fabricated.

Furthermore, Samples G3 to G5 were fabricated as comparative examples.

<Sample G1>

FIG. 63A is a cross-sectional view in the channel length direction ofthe transistor included in Sample G1. The transistor illustrated in FIG.63A is a channel-etched transistor. The space between the pair ofelectrodes 19 and 20 was 6 μm.

A method for fabricating Sample G1 is described. Sample G1 wasfabricated in a manner similar to that of Sample C1 described in Example6 except for high-frequency power supplied to parallel plate electrodesfor forming the first oxide insulating film (reference numeral 23 inFIG. 63A). Specifically, a sample including a first oxide insulatingfilm formed under the following conditions was fabricated as Sample G1.

A first oxide insulating film in Sample G1 was formed by a plasma CVDmethod under the following conditions: silane with a flow rate of 50sccm and dinitrogen monoxide with a flow rate of 2000 sccm were used asa source gas; the pressure in the treatment chamber was 20 Pa; thesubstrate temperature was 220° C.; and a high-frequency power of 150 Wwas supplied to parallel-plate electrodes.

Note that the measurement result of V_(g)-I_(d) characteristics showsthat the transistor included in Sample G1 has normally-offcharacteristics.

<Sample G2>

FIG. 63B is a cross-sectional view in the channel length direction ofthe transistor included in Sample G2. The transistor illustrated in FIG.63B is a channel-etched transistor. The space between the pair ofelectrodes 19 and 20 was 6 μm.

Sample G2 is different from Sample G1 in that the gate electrode 37 isprovided over the protective film 21. Although not illustrated, the gateelectrode 37 is connected to the gate electrode 13.

A method for fabricating Sample G2 is described. Sample G2 wasfabricated in a manner similar to that of Sample G1 except that, afteran opening portion was formed in the gate insulating film 15 and theprotective film 21, the gate electrode 37 was formed at the same time asa pixel electrode.

Note that the measurement result of V_(g)-I_(d) characteristics showsthat the transistor included in Sample G2 has normally-offcharacteristics.

<Sample G3>

FIG. 63C is a cross-sectional view in the channel length direction ofthe transistor included in Sample G3. The transistor illustrated in FIG.63C is a channel-etched transistor. The space between the pair ofelectrodes 19 and 20 was 6 μm.

Sample G3 is different from Sample G1 in that the multilayer film 48 inwhich the oxide semiconductor film 17 and the oxide semiconductor film46 were stacked and a first oxide insulating film 23 a that was formedunder conditions different from those of the first oxide insulating film(reference numeral 23 in FIG. 63A) were included.

A method for fabricating Sample G3 is described.

The oxide semiconductor film 46 was formed under the followingconditions: a sputtering target containing In, Ga, and Zn at an atomicratio of 1:3:6 was used, oxygen at a flow proportion of 50% was suppliedas a sputtering gas into a treatment chamber of a sputtering apparatus;the pressure in the treatment chamber was controlled to 0.6 Pa; anddirect-current power of 2.5 kW was supplied. Note that the oxidesemiconductor film was formed at a substrate temperature of 170° C.

The first oxide insulating film 23 a was formed by a plasma CVD methodunder the following conditions: same with a flow rate of 30 sccm anddinitrogen monoxide with a flow rate of 4000 sccm were used as a sourcegas; the pressure in the treatment chamber was 40 Pa; the substratetemperature was 220° C.; and a high-frequency power of 150 W wassupplied to parallel-plate electrodes.

Other conditions were similar to those of Sample G1.

Note that the measurement result of V_(g)-I_(d) characteristics showsthat the transistor included in Sample G1 is a normally-off transistor.

<Sample G4>

FIG. 63D is a cross-sectional view in the channel length direction ofthe transistor included in Sample G4. The transistor illustrated in FIG.63D is a channel-etched transistor. The shortest distance between thepair of electrodes 219 and 220 was 9 μm.

The transistor included in Sample G4 includes a gate electrode 213provided over a substrate 211, a gate insulating film 215 formed overthe substrate 211 and the gate electrode 213, an oxide semiconductorfilm 217 overlapping with the gate electrode 213 with the gateinsulating film 215 provided therebetween, and a pair of electrodes 219and 220 in contact with the oxide semiconductor film 217. Furthermore, aprotective film 221 is formed over the gate insulating film 215, theoxide semiconductor film 217, and the pair of electrodes 219 and 220.

The substrate 211 is formed of a glass substrate. In the gate electrode213, a titanium film and a copper film are stacked in this order fromthe substrate 211 side. In the gate insulating film 215, a siliconnitride film and a silicon oxide film are stacked in this order from thesubstrate 211 side. The oxide semiconductor film 217 is formed using anIn—Ga—Zn oxide film. The oxide semiconductor film 217 is ananocrystalline oxide semiconductor film. In each of the pair ofelectrodes 219 and 220, a titanium film and a copper film are stacked inthis order from the substrate 211 side. The protective film 221 isformed using a silicon oxide film.

Note that the measurement result of V_(g)-I_(d) characteristics showsthat the transistor included in Sample G4 has normally-offcharacteristics.

<Sample G5>

FIG. 63E is a cross-sectional view in the channel length direction ofthe transistor included in Sample G5. The transistor illustrated in FIG.63E is a channel protective transistor. The space between regions wherea pair of electrodes 241 and 242 are in contact with an oxidesemiconductor film 237 is 10.5 μm.

The transistor included in Sample G5 includes a gate electrode 233provided over a substrate 231, a gate insulating film 235 formed overthe substrate 231 and the gate electrode 233, the oxide semiconductorfilm 237 overlapping with the gate electrode 233 with the gateinsulating film 235 provided therebetween, an insulating film 239 formedover the gate insulating film 235 and the oxide semiconductor film 237,and the pair of electrodes 241 and 242 in contact with the oxidesemiconductor film 237 in an opening portion of the insulating film 239.The transistor also includes a gate insulating film 243 formed over theinsulating film 239 and the pair of electrodes 241 and 242 and a gateelectrode 245 overlapping with the oxide semiconductor film 237 with thegate insulating film 243 provided therebetween.

The substrate 231 is formed of a glass substrate. In the gate electrode233, a molybdenum-titanium alloy film and a copper film are stacked inthis order from the substrate 231 side. In the gate insulating film 235,a silicon nitride film and a silicon oxide film are stacked in thisorder from the substrate 231 side. The oxide semiconductor film 237 isformed using an In—Ga—Zn oxide film. The oxide semiconductor film 237 isa nanocrystalline oxide semiconductor film. The insulating film 239 isformed using a silicon oxide film. In each of the pair of electrodes 241and 242, a molybdenum-titanium alloy film and a copper film are stackedin this order from the substrate 231 side. The gate insulating film 243is formed using a silicon oxide film. In the gate electrode 245, amolybdenum-titanium alloy film and an indium oxide-tin oxide compound(ITO-SiO2) film are stacked in this order from the substrate 231 side.

Note that the measurement result of V_(g)-I_(d) characteristics showsthat the transistor included in Sample G5 has normally-oncharacteristics.

<Sample G6>

FIG. 63B is a cross-sectional view in the channel length direction ofthe transistor included in Sample G6. The transistor illustrated in FIG.63B is a channel-etched transistor. The space between the pair ofelectrodes 19 and 20 was 6 μm.

Sample G6 differs from Sample G2 in the composition of the oxidesemiconductor film.

A method for fabricating Sample G6 is described. Sample G6 wasfabricated in a manner similar to that of Sample G2 except that theoxide semiconductor film was formed using a sputtering target containingIn, Ga, and Zn at an atomic ratio of 1:1:1.2.

Note that the measurement result of V_(g)-I_(d) characteristics showsthat the transistor included in Sample G6 is has normally-oncharacteristics.

<BT Stress Test>

Then, BT stress tests were performed on the transistors included inSamples G1 to G5.

Here, positive gate BT stress tests (dark +GBT) were performed. The gateBT stress conditions were as follows: stress temperature was 60° C., +30V was applied to the gate electrode(s), and 0 V was applied to the pairof electrodes serving as the source electrode and the drain electrode.

In Samples G1, G3, and G4, the amounts of change in threshold voltageswere measured with a maximum stress time of 1 hour. In Sample G2, theamount of change in threshold voltage was measured with a maximum stresstime of 100 hours. In Sample G5, the amount of change in thresholdvoltage was measured with a maximum stress time of 24 hours. In SampleG6, the amount of change in threshold voltage was measured with amaximum stress time of 10 hours.

FIGS. 64A to 64D show measurement results of the initial V_(g)-I_(d)characteristics of Samples G2 to G5 and V_(g)-I_(d) characteristics witha stress time of one hour.

FIG. 64A, FIG. 64B, FIG. 64C, and FIG. 64D show the measurement resultsof the V_(g)-I_(d) characteristics of Sample G2, Sample G3, Sample G4,and Sample G5, respectively. In FIGS. 64A to 64D, solid lines and dashedlines indicate the initial V_(g)-I_(d) characteristics and theV_(g)-I_(d) characteristics with a stress time of one hour,respectively, Note that in FIGS. 64A and 64D showing the measurementresults of Samples G2 and G5, the amounts of change in the thresholdvoltages before and after a stress test were small with a stress time ofone hour; thus, solid lines overlap with dashed lines.

FIG. 65 shows measurement results of the absolute values of the amountsof change in the threshold voltages with respect to stress time.Specifically, FIG. 65 shows the absolute values of the amounts of changein the threshold voltages of the transistors included in Samples G1 toG6, and approximate curves obtained from the absolute values of theamounts of change. Note that the lateral axis indicates stress time andthe longitudinal axis indicates the absolute value (|ΔV_(th)|) of theamount of change in threshold voltage. In FIG. 65, black squares, blackcircles, white squares, white rhombuses, white triangles, and blacktriangles indicate measurement data of Sample G1, Sample G2, Sample G3,Sample G4, Sample G5, and Sample G6, respectively. In addition, solidlines are power approximation lines obtained from the measurement dataof Samples G1 and G2, and dashed lines are power approximation linesobtained from the measurement data of Samples G3 to G5.

The index of the power approximation line of Sample G1 was 0.29. Theindex of the power approximation line of Sample G2 was 0.19. The indexof the power approximation line of Sample G3 was 0.32. The index of thepower approximation line of Sample G4 was 0.42. The index of the powerapproximation line of Sample G5 was 0.56.

The absolute value of the threshold voltage of each of Samples G1, G2,and G5 with a stress time of 0.1 hours was lower than or equal to 0.1 V.At the same time, Samples G1 and G2 have lower index of the powerapproximation line than Sample G5. Accordingly, the longer the stresstime is, the more the absolute value of the amount of change in thethreshold voltage increases in Sample G5 and the less the absolute valueof the amount of change in the threshold voltage increases in Samples G1and G2.

The above results show that the transistor of one embodiment of thepresent invention is a highly reliable transistor with a small change inthreshold voltage over time.

<Repeated ±Gate BT Stress Test>

Next, gate BT stress tests were repeatedly performed on Samples G2, G4,G5, and G6 in a dark state.

Repeated ±gate BT stress test is described. First, the stresstemperature of a sample is set at 60° C. and the V_(g)-I_(d)characteristics of a transistor are measured. Next, a +gate BT stresstest is performed. Here, +30 V is applied to a gate electrode for onehour. Then, the V_(g)-I_(d) characteristics of the transistor aremeasured while the temperature is kept at 60° C. Subsequently, a −gateBT stress test is performed. Here, −30 V is applied to the gateelectrode for one hour while the sample is kept at 60° C. Next, theV_(g)-I_(d) characteristics of the transistor are measured while thetemperature is kept at 60° C. Repeating the +gate BT stress test and the−gate BT stress test enables the change in threshold voltage to bemeasured.

FIG. 66 shows the results of the repeated ±gate BT stress tests. Thelateral axis indicates stress tests and the longitudinal axis indicatesthe threshold voltage. In FIG. 66, black circles, white rhombuses, whitetriangles, and black triangles indicate measurement data of Sample G2,Sample G4, Sample G5, and Sample G6, respectively.

As shown in FIG. 66, the change in threshold voltage due to the repeated±gate BT stress tests is large in Sample G4. In Sample G5, although thechange in threshold voltage due to the repeated ±gate BT stress tests issmall, the threshold voltage is a negative value thus, the transistorhas normally-on characteristics. In contrast, since the changes inthreshold voltages are small and the threshold voltages are positivevalues in Samples G2 and G6, the transistors have normally-offcharacteristics.

The above results show that the transistor of one embodiment of thepresent invention is a highly reliable transistor with a small change inthreshold voltage over time. The results also show that the transistorof one embodiment of the present invention has normally-offcharacteristics. For this reason, a semiconductor device including thetransistor of one embodiment of the present invention consumes lowpower.

EXAMPLE 8

Described in this example is the diffusion of oxygen in an oxideinsulating film that is in contact with an oxide semiconductor film andhas a stacked-layer structure like the oxide insulating film describedin Modification Example 1 in Embodiment 1. In this example, the oxygenconcentration was measured by SSDP-SIMS (SIMS measurement from thesubstrate side) to describe the diffusion of oxygen

<Sample D1>

A method for fabricating Sample D1 is described.

First, a 100-nm-thick oxide semiconductor film (IGZO in FIGS. 67A and67B) was formed over a glass substrate (“Glass” in FIGS. 67A and 67B) bya sputtering method using an In—Ga—Zn oxide sputtering target whereIn:Ga:Zn=1:1:1 (atomic ratio) and using oxygen and argon as sputteringgases.

Next, a first oxide insulating film (“SiON” in FIGS. 67A and 67B) and asecond oxide insulating film (“SP-SiO,” in FIGS. 67A and 67B) wereformed over the oxide semiconductor film. As the second oxide insulatingfilm, a silicon oxide film containing oxygen at a higher proportion thanoxygen in the stoichiometric composition was formed.

Here, as the first oxide insulating film, a 30-nm-thick siliconoxynitride film was formed by a plasma CVD method under the followingconditions: silane at a flow rate of 30 sccm and dinitrogen monoxide ata flow rate of 4000 sccm were used as a source gas, the pressure in thetreatment chamber was 200 Pa, the substrate temperature was 220° C., anda high-frequency power of 150 W was supplied to parallel-plateelectrodes.

As the second oxide insulating film, a 100-nm-thick silicon oxide filmcontaining ¹⁸O was formed by a sputtering method in which a siliconwafer was placed in a treatment chamber of a sputtering apparatus, and¹⁸O (an isotope of ¹⁶O) with a flow rate of 300 sccm as a source gas wassupplied to the treatment chamber.

Through the above process, Sample D1 was fabricated.

<Sample D2>

A method for fabricating Sample D2 is described.

Sample D1 was heated at 350° C. in an atmosphere of a mixed gascontaining nitrogen and oxygen for one hour.

Through the above process, Sample D2 was fabricated.

<SIMS Analysis>

Next, the concentration profiles of ¹⁸O contained in the first oxideinsulating films SiON and the oxide semiconductor films IGZO of SamplesD1 and D2 were measured by SIMS. Here, the concentration of ¹⁸O wasmeasured from the glass substrate side to the second oxide insulatingfilm.

FIGS. 67A and 67B each show the concentration profiles of ¹⁸O that wereobtained by the SIMS measurement. The first oxide insulating film SiONwas quantified and the results are shown in FIG. 67A, and the oxidesemiconductor film IGZO was quantified and the results are shown in FIG.67B. In FIGS. 67A and 67B, thin solid line and the hold solid lineindicate the measurement results of Samples D1 and D2. respectively.

As shown in FIG. 67A, the concentration of ¹⁸O increases in the firstoxide insulating film SiON in Sample D2, As shown in FIG. 67B, theconcentration of ¹⁸O increases in the oxide semiconductor film IGZO onthe first oxide insulating film SiON side in Sample D2.

The above results indicate that oxygen is diffused by heat treatmentfrom the second oxide insulating film SP-SiO, through the first oxideinsulating film SiON to the oxide semiconductor film IGZO.

EXAMPLE 9

Described in this example are heat treatment and the number of oxygenvacancies in an oxide insulating film that is in contact with an oxidesemiconductor film and has a stacked-layer structure like the oxideinsulating film described in Modification Example 1 in Embodiment 1. Inthis example, the number of oxygen vacancies in the oxide semiconductorfilm is described using the measurement results of ESR.

<Sample E1>

A method for fabricating Sample E1 is described.

First, a 35-nm-thick oxide semiconductor film was formed over a quartzsubstrate by a sputtering method using an In—Ga—Zn oxide sputteringtarget where In:Ga:Zn=1:1:1 (the ratio of the number of atoms) and usinga sputtering gas of oxygen and argon.

Next, heat treatment was performed at 450° C. in a nitrogen atmospherefor one hour, and then another heat treatment was performed at 450° C.in a mixed gas of nitrogen and oxygen for one hour.

Next, a first oxide insulating film and a second oxide insulating filmwere formed over the oxide semiconductor film. As the second oxideinsulating film, a silicon oxynitride film containing oxygen at a higherproportion than oxygen in the stoichiometric composition was formed.

Here, as the first oxide insulating film, a 50-nm-thick siliconoxynitride film was formed. The first oxide insulating film was formedby a plasma CVD method under the following conditions: silane at a flowrate of 30 sccm and dinitrogen monoxide at a flow rate of 4000 sccm wereused as a source gas, the pressure in the treatment chamber was 40 Pa,the substrate temperature was 220° C., and a high-frequency power of 150W was supplied to parallel-plate electrodes.

As the second oxide insulating film, a 400-nm-thick silicon oxynitridefilm was formed. The second oxide insulating film was formed by a plasmaCVD method under the following conditions: silane at a flow rate of 160sccm and dinitrogen monoxide at a flow rate of 4000 sccm were used as asource gas, the pressure in the treatment chamber was 200 Pa, thesubstrate temperature was 220° C., and a high-frequency power of 1500 Wwas supplied to parallel-plate electrodes.

Through the above process, Sample E1 was fabricated.

<Sample E2>

A method for forming Sample E2 is described.

Sample E1 was heated at 350° C. in an atmosphere of a mixed gascontaining nitrogen and oxygen for one hour.

Through the above process, Sample E2 was formed.

<ESR Measurement>

Next, Samples E1 and E2 were measured by ESR measurement. In the ESRmeasurement performed at a predetermined temperature, a value of amagnetic field (H₀) where a microwave is absorbed is used for anequation g=hv/βH₀; thus, a parameter “g-factor” can be obtained. Notethat the frequency of the microwave is denoted by v, and the Planckconstant and the Bohr magneton are denoted by, respectively, h and βthat are both constants.

Here, the ESR measurement was performed under the following conditions.Here, the ESR measurement was performed under the following conditions:the measurement temperature was room temperature (25° C.), thehigh-frequency power (power of microwaves) of 8.9 GHz was 20 mW, and thedirection of a magnetic field was parallel to a surface of each sample.Note that the detection limit of the spin density of a signal attributedto V_(O)H in the IGZO film, which appeared at a g (g-factor) of greaterthan or equal to 1.89 and less than or equal to 1.96, was 1×10¹⁷spins/cm³.

FIGS. 68A and 68B show ESR spectra obtained by ESR measurement. FIGS.68A and 68B show ESR spectra of the oxide semiconductor films of SamplesE1 and E2, respectively.

As shown in FIG. 68A, in Sample E1, a signal attributed to V_(O)Happears at a g (g-factor) of 1.93. The number of spins absorbed at a g(g-factor) of 1.93 is 5.14×10¹⁸ spins/cm³. This means that the oxidesemiconductor film contains V_(O)H.

In contrast, as shown in FIG. 68B, in Sample E2, a signal attributed toV_(O)H appearing at a g (g-factor) of 1.93 is not observed.

The difference between the signals that appear at a g (g-factor) of 1.93in FIGS. 68A and 68B confirmed that V_(O)H in the oxide semiconductorfilm can be reduced by heat treatment. Furthermore, the resultsdescribed in Example 8 reveal that oxygen contained in the oxideinsulating film containing oxygen at a higher proportion than oxygen inthe stoichiometric composition is diffused to the oxide semiconductorfilm by heat treatment. This means that when oxygen is diffused to theoxide semiconductor film by heat treatment, V_(O)H in the oxidesemiconductor film can be reduced.

EXAMPLE 10

In this example, oxidizing power of plasma caused when an oxideinsulating film was exposed to plasma generated by using dinitrogenmonoxide or oxygen as an oxidizing gas is described.

First, a method of fabricating each sample is described.

A 100-nm-thick silicon oxynitride film was formed as an oxide insulatingfilm containing nitrogen over a quartz substrate. Then, the siliconoxynitride film was exposed to plasma that was generated in an oxidizinggas atmosphere. Conditions of the formation of the silicon oxynitridefilm and conditions of plasma treatment are described below.

The silicon oxynitride film was formed under the conditions as follows:the quartz substrate was placed in a treatment chamber of a plasma CVDapparatus; silane with a flow rate of 1 sccm and dinitrogen monoxidewith a flow rate of 800 sccm that were used as a source gas weresupplied to the treatment chamber; the pressure in the treatment chamberwas controlled to 40 Pa: and the power of 150 W was supplied with theuse of a 60 MHz high-frequency power source. Further, the temperature ofthe quartz substrate at the formation of the silicon oxynitride film was400° C. Note that the plasma CVD apparatus used in this example is aparallel plate plasma CVD apparatus in which the electrode area is 615cm², and the power per an it area (power density) into which thesupplied power is converted is 0.24 W/cm².

Plasma was generated in such a manner that dinitrogen monoxide or oxygenwith a flow rate of 900 sccm was supplied to the treatment chamber, thepressure in the treatment chamber was controlled to 200 Pa, and power of900 W (1.46 W/cm²) was supplied with the use of a 60 MHz high-frequencypower source. Further, the temperature of the quartz substrate at thetime of plasma generation was 200° C. Here, a sample that was exposed toplasma generated in a dinitrogen monoxide atmosphere is referred to asSample F1. In addition, a sample that was exposed to plasma generated inan oxygen atmosphere is referred to as Sample F2.

Next, TDS analyses were performed on Samples F1 and F2.

The peaks of the curves shown in the results obtained from TDS analysesappear due to release of atoms or molecules contained in the analyzedsamples (in this example, Samples F1 and F2) to the outside. The totalamount of the atoms or molecules released to the outside corresponds tothe integral value of the peak. Thus, with the degree of the peakintensity, the number of the atoms or molecules contained in the siliconoxynitride film can be evaluated.

FIGS. 69A and 69B show the results of the TDS analyses on Samples F1 andF2. FIGS. 69A and 69B are each a graph showing the number of releasedoxygen molecules versus the substrate temperature.

FIGS. 69A and 69B demonstrate that the silicon oxynitride film that wasexposed to plasma generated in a dinitrogen monoxide atmosphere hashigher TDS intensity of oxygen molecules than the silicon oxynitridefilm that was exposed to plasma generated in an oxygen atmosphere. Asdescribed above, plasma generated in a dinitrogen monoxide atmospherehas stronger oxidizing power than plasma generated in an oxygenatmosphere and enables formation of a film containing excess oxygen,from which oxygen is released easily by heating.

Accordingly, in the case where an oxide insulating film is formed overan oxide semiconductor film by a plasma CVD method, a film containingexcess oxygen, from which oxygen can be released by heating, can beformed by using a deposition gas containing silicon and dinitrogenmonoxide as a source gas. Note that when dinitrogen monoxide is used asa source gas, nitrogen is contained in the oxide insulating film;therefore, an oxide insulating film containing nitrogen and excessoxygen can be obtained.

EXPLANATION OF REFERENCE

10: transistor, 10 a: transistor, 10 b: transistor, 10 c: transistor, 10d: transistor, 10 e: transistor, 10 f: transistor, 10 g: transistor, 10h: transistor, 10 i: transistor, 10 j: transistor, 10 k: transistor, 11:substrate, 13: gate electrode, 15: gate insulating film, 17: oxidesemiconductor film, 17 a: oxide semiconductor film, 19: electrode, 19 a:electrode, 20: electrode, 20 a: electrode, 21: protective film, 22:insulating film, 23: oxide insulating film, 23 a: oxide insulating film,25: oxide insulating film, 27: nitride insulating film, 29: nitrideinsulating film, 31: oxide insulating film, 33: insulating film, 35:insulating film, 37: gate electrode, 38: organic insulating film, 42:opening portion, 43: opening portion, 45: multilayer film, 46: oxidesemiconductor film, 47: oxide semiconductor film, 48: multilayer film,50: transistor, 50 a: transistor, 50 b: transistor, 50 c: transistor,51: substrate, 53: protective film, 55: oxide semiconductor film, 57:electrode, 58: electrode, 59: gate insulating film, 61: gate electrode,63: insulating film, 65: oxide insulating film, 67: oxide insulatingfilm, 69: oxide insulating film, 71: nitride insulating film, 73: oxidesemiconductor film, 75: oxide semiconductor film, 80: pixel electrode,81: substrate, 82: common electrode, 83: liquid crystal layer, 84:insulating film, 85: insulating film, 86: light-emitting layer, 110:metal oxide film, 211: substrate, 213: gate electrode, 215: gateinsulating film, 217: oxide semiconductor film, 219: electrode, 220:electrode, 221: protective film, 231: substrate, 233: gate electrode,235: gate insulating film, 237: oxide semiconductor film, 239:insulating film, 241: electrode, 242: electrode, 243: gate insulatingfilm, 245: gate electrode, 310: electron gun chamber, 312: opticalsystem, 314: sample chamber, 316: optical system, 318: camera, 320:observation chamber, 322: film chamber, 324: electron, 328: substance,332: fluorescent plate, 900: substrate, 901: pixel portion, 902:scanning line driver circuit, 903: scanning line driver circuit, 904:signal line driver circuit, 910: capacitor wiring, 912: gate wiring,913: gate wiring, 914: drain electrode, 916: transistor, 917:transistor, 918: liquid crystal element, 919: liquid crystal element,920: pixel, 921: switching transistor, 922: driver transistor, 923:capacitor, 924: light-emitting element, 925: signal line, 926: scanline, 927: power line, 928: common electrode, 1001: main body, 1002:housing, 1003 a: display portion, 1003 b: display portion, 1004:keyboard button, 1021: main body, 1022: fixing portion, 1023: displayportion, 1024: operation button, 1025: external memory slot, 1030:housing, 1031: housing, 1032: display panel, 1033: speaker, 1034:microphone, 1035: operation key, 1036: pointing device, 1037: cameralens, 1038: external connection terminal, 1040: solar cell, 1041:external memory slot, 1050: television device, 1051: housing, 1052:storage medium recording and reproducing portion, 1053: display portion,1054: external connection terminal, 1055: stand, 1056: external memory,5100: pellet, 5100 a: pellet, 5100 b: pellet, 5101: ion, 5102: zincoxide layer, 5103: particle, 5105 a: pellet, 5105 a 1: region, 5105 a 2:pellet, 5105 b: pellet, 5105 c: pellet, 5105 d: pellet, 5105 d 1:region, 5105 e: pellet, 5120: substrate, 5130: target, 5161: region,8000: display module, 8001: upper cover, 8002: lower cover, 8003: FPC,8004: touch panel, 8005: FPC, 8006: display panel, 8007: backlight unit,8008: light source, 8009: frame, 8010: printed board, and 8011: battery.

This application is based on Japanese Patent Application serial no.2013-213240 filed with Japan Patent Office on Oct. 10, 2013, JapanesePatent Application serial no. 2013-216220 filed with Japan Patent Officeon Oct. 17, 2013, Japanese Patent Application serial no. 2013-242253filed with Japan Patent Office on Nov. 22, 2013, and Japanese PatentApplication serial no. 2013-250040 filed with Japan Patent Office onDec. 3, 2013, the entire contents of which are hereby incorporated byreference.

The invention claimed is:
 1. A semiconductor device comprising: an oxidesemiconductor layer and a first electrode overlapping with each other;an insulating layer between the first electrode and the oxidesemiconductor layer, the insulating layer being in contact with theoxide semiconductor layer; and a pair of second electrodes in electricalcontact with the oxide semiconductor layer, wherein the insulating layerincludes silicon, oxygen, and nitrogen oxide, wherein the insulatinglayer includes a portion whose spin density measured by electron spinresonance spectroscopy is greater than or equal to 1×10¹⁷ spins/cm³ andless than 1×10¹⁸ spins/cm³, wherein an electron spin resonance spectrumof the portion has a first signal that appears at a g-factor in a rangegreater than or equal to 2.037 and less than or equal to 2.039, a secondsignal that appears at a g-factor in a range greater than or equal to2.001 and less than or equal to 2.003, and a third signal that appearsat a g-factor in a range greater than or equal to 1.964 and less than orequal to 1.966, and wherein the first signal, the second signal, and thethird signal are attributed to the nitrogen oxide.
 2. The semiconductordevice according to claim 1, wherein the insulating layer includes aregion where an amount of gas having a mass-to-charge ratio m/z of 17released by heat treatment is greater than an amount of nitrogen oxidereleased by the heat treatment.
 3. The semiconductor device according toclaim 2, wherein at least one of an amount of gas having amass-to-charge ratio m/z of 30 released by the heat treatment and anamount of gas having a mass-to-charge ratio m/z of 46 released by theheat treatment is less than or equal to a detection limit in the region,and wherein the amount of the gas having the mass-to-charge ratio m/z of17 released by the heat treatment is greater than or equal to 1×10¹⁸molecules/cm³ and less than or equal to 5×10¹⁹ molecules/cm³ in theregion.
 4. The semiconductor device according to claim 3, wherein thegas having the mass-to-charge ratio m/z of 30 comprises nitrogenmonoxide, wherein the gas having the mass-to-charge ratio m/z of 46comprises nitrogen dioxide, and wherein the gas having themass-to-charge ratio m/z of 17 comprises ammonia.
 5. The semiconductordevice according to claim 1, wherein a split width of the first signaland the second signal and a split width of the second signal and thethird signal measured by electron spin resonance spectroscopy using anX-band are each 5 mT.
 6. The semiconductor device according to claim 1,wherein the nitrogen oxide includes at least one of nitrogen monoxideand nitrogen dioxide.
 7. The semiconductor device according to claim 1,wherein the first electrode is over an insulating surface, and whereinthe oxide semiconductor layer, and the insulating layer are between theinsulating surface and the first electrode.
 8. The semiconductor deviceaccording to claim 1, wherein the first electrode is over an insulatingsurface, and wherein the first electrode and the insulating layer arebetween the insulating surface and the oxide semiconductor layer.
 9. Thesemiconductor device according to claim 1, wherein the insulating layeris in direct contact with the oxide semiconductor layer.
 10. Thesemiconductor device according to claim 2, wherein the region includes afirst number of ammonia molecules and a second number of nitrogen oxidemolecules so that the amount of the gas having the mass-to-charge ratiom/z of 17 released by the heat treatment is greater than the amount ofnitrogen oxide released by the heat treatment.
 11. A semiconductordevice comprising: an oxide semiconductor layer and a first electrodeoverlapping with each other; a first insulating layer between the firstelectrode and the oxide semiconductor layer, the first insulating layerbeing in contact with a first surface of the oxide semiconductor layer;a second insulating layer in contact with a second surface of the oxidesemiconductor layer, the second surface being on a side opposite to thefirst surface; and a pair of second electrodes in electrical contactwith the oxide semiconductor layer, wherein the second insulating layerincludes silicon, oxygen, and nitrogen oxide, wherein the secondinsulating layer includes a portion whose spin density measured byelectron spin resonance spectroscopy is greater than or equal to 1×10¹⁷spins/cm³ and less than 1×10¹⁸ spins/cm³, wherein an electron spinresonance spectrum of the portion has a first signal that appears at ag-factor in a range greater than or equal to 2.037 and less than orequal to 2.039, a second signal that appears at a g-factor in a rangegreater than or equal to 2.001 and less than or equal to 2.003, and athird signal that appears at a g-factor in a range greater than or equalto 1.964 and less than or equal to 1.966, and wherein the first signal,the second signal, and the third signal are attributed to the nitrogenoxide.
 12. The semiconductor device according to claim 11, wherein thesecond insulating layer includes a region where an amount of gas havinga mass-to-charge ratio m/z of 17 released by heat treatment is greaterthan an amount of nitrogen oxide released by the heat treatment.
 13. Thesemiconductor device according to claim 12, wherein at least one of anamount of gas having a mass-to-charge ratio m/z of 30 released by theheat treatment and an amount of gas having a mass-to-charge ratio m/z of46 released by the heat treatment is less than or equal to a detectionlimit in the region, and wherein the amount of the gas having themass-to-charge ratio m/z of 17 released by the heat treatment is greaterthan or equal to 1×10¹⁸ molecules/cm³ and less than or equal to 5×10¹⁹molecules/cm³ in the region.
 14. The semiconductor device according toclaim 13, wherein the gas having the mass-to-charge ratio m/z of 30comprises nitrogen monoxide, wherein the gas having the mass-to-chargeratio m/z of 46 comprises nitrogen dioxide, and wherein the gas havingthe mass-to-charge ratio m/z of 17 comprises ammonia.
 15. Thesemiconductor device according to claim 11, wherein a split width of thefirst signal and the second signal and a split width of the secondsignal and the third signal measured by electron spin resonancespectroscopy using an X-band are each 5 mT.
 16. The semiconductor deviceaccording to claim 11, wherein the nitrogen oxide includes at least oneof nitrogen monoxide and nitrogen dioxide.
 17. The semiconductor deviceaccording to claim 11, wherein the first electrode is over an insulatingsurface, and wherein the second insulating layer, the oxidesemiconductor layer, and the first insulating layer are between theinsulating surface and the first electrode.
 18. The semiconductor deviceaccording to claim 11, wherein the first electrode is over an insulatingsurface, and wherein the first electrode and the first insulating layerare between the insulating surface and the oxide semiconductor layer.19. The semiconductor device according to claim 11, wherein the firstinsulating layer is in direct contact with the first surface of theoxide semiconductor layer, and wherein the second insulating layer is indirect contact with the second surface of the oxide semiconductor layer.20. The semiconductor device according to claim 12, wherein the regionincludes a first number of ammonia molecules and a second number ofnitrogen monoxide molecules so that the amount of the gas having themass-to-charge ratio m/z of 17 released by the heat treatment is greaterthan the amount of the gas having the mass-to-charge ratio m/z of 30released by the heat treatment.